WO2022190951A1 - Methacrylic resin composition for hot-plate welding, use in hot-plate welding of methacrylic resin composition for hot-plate welding, welding method, and member for vehicle - Google Patents
Methacrylic resin composition for hot-plate welding, use in hot-plate welding of methacrylic resin composition for hot-plate welding, welding method, and member for vehicle Download PDFInfo
- Publication number
- WO2022190951A1 WO2022190951A1 PCT/JP2022/008537 JP2022008537W WO2022190951A1 WO 2022190951 A1 WO2022190951 A1 WO 2022190951A1 JP 2022008537 W JP2022008537 W JP 2022008537W WO 2022190951 A1 WO2022190951 A1 WO 2022190951A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hot plate
- resin composition
- methacrylic resin
- plate welding
- fatty acid
- Prior art date
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- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
- B29C65/20—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools with direct contact, e.g. using "mirror"
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- C—CHEMISTRY; METALLURGY
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
Definitions
- the present invention relates to a methacrylic resin composition for hot plate welding, use of the methacrylic resin composition for hot plate welding in hot plate welding, a welding method, and a vehicle member.
- This application claims priority based on Japanese Patent Application No. 2021-036914 filed in Japan on March 9, 2021, the content of which is incorporated herein.
- methacrylic resins are used as vehicle parts such as tail lamp covers, head lamp covers, meter panels, and other vehicle interior and exterior materials; building materials; , bathtubs, flush toilets, and other housing equipment.
- a methacrylic resin is used for these purposes, such a member is joined with a member made of a styrene resin such as an MS resin or an ABS resin, or a resin other than a methacrylic resin such as a polycarbonate resin, and processed. .
- a hot plate fusion method is known as a method for joining these members (Patent Documents 1 to 4).
- each member is heated and melted by bringing the joint surface of each member into close contact with a metal hot plate. It is a method of joining by welding (crimping), and high welding strength can be obtained.
- the hot plate fusion method is capable of welding large parts together, and has the advantage of eliminating the time and effort required to apply adhesive and harden the adhesive. is an excellent method for
- the purpose of the present invention is to solve these problems. That is, the object of the present invention is to prevent stringing from occurring when the resin composition is separated from the hot plate during hot plate fusion, and to prevent the resin composition from leaving residue on the mold surface during injection molding.
- the object of the present invention is to provide a methacrylic resin composition for hot plate welding suitable for hot plate welding.
- the present inventors have arrived at the present invention as a result of repeated studies to solve the above problems. That is, the present invention includes the following aspects.
- a methacrylic resin composition for hot plate welding containing a methacrylic polymer and a fatty acid.
- the methacrylic polymer contains a repeating unit derived from methyl methacrylate, and the content of the repeating unit derived from methyl methacrylate in the methacrylic polymer is 70% by mass or more, [1] to [ 9], the methacrylic resin composition for hot plate welding.
- the methacrylic polymer is a polymer (A) containing a repeating unit derived from a (meth)acrylate monomer and a structural unit derived from a ring structure,
- the structural unit derived from the ring structure contains at least one selected from a glutaric anhydride structural unit, a maleic anhydride structural unit, a glutarimide structural unit, a lactone ring structural unit, and an N-substituted maleimide structural unit, [ The methacrylic resin composition for hot plate welding according to any one of 1] to [10].
- the polymer (A) comprises a repeating unit (A1) derived from methyl methacrylate, a repeating unit (A2) derived from (meth)acrylic acid, and a glutaric anhydride structural unit (A3), [11 ] methacrylic resin composition for hot plate welding.
- A1 derived from methyl methacrylate
- A2 derived from (meth)acrylic acid
- A3 glutaric anhydride structural unit
- methacrylic resin composition for hot plate welding according to any one of [1] to [12], which is used as a raw material for vehicle members.
- the methacrylic resin composition for hot plate welding according to [13] wherein the vehicle member is at least one selected from a tail lamp cover, a head lamp cover, and a meter panel.
- a vehicle member including a composite member formed by bonding a first member and a second member, A vehicle member, wherein the first member contains a methacrylic polymer and a fatty acid.
- stringing is less likely to occur when the resin composition is separated from the hot plate during hot plate fusion, and peeling residue of the resin composition is less likely to occur on the mold surface during injection molding. It is possible to provide a methacrylic resin composition for hot plate welding suitable for hot plate welding.
- FIG. 2 is a schematic diagram showing a state in which a conical test piece is stringing in a stringing test.
- (meth)acrylate means at least one selected from “acrylate” and “methacrylate”
- “(meth)acrylic acid” is selected from “acrylic acid” and "methacrylic acid”.
- “monomer” means an unpolymerized compound
- “repeating unit” means a unit derived from a monomer formed by polymerizing the monomer.
- the repeating unit may be a unit directly formed by a polymerization reaction, or may be a part of the unit converted to another structure by treating the polymer.
- “% by mass” indicates the content ratio of a given component contained in 100% by mass of the total amount.
- the "obtained resin molded article” means a molded article obtained by molding a methacrylic resin composition for hot plate welding.
- a numerical range represented by “to” means a range including the numerical values before and after "to” as lower and upper limits.
- methacrylic resin composition for hot plate welding of the present invention contains a methacrylic polymer and a fatty acid.
- the melt flow rate (MFR) of the methacrylic resin composition of the present invention is not particularly limited.
- the MFR measured at a temperature of 230 ° C. and a load of 3.8 kg is preferably 0.1 to 10 g / 10 min, more preferably 0.2 to 5 g / 10 min.
- 0.3 to 2 g/10 min is more preferable. Since the MFR is equal to or less than the above upper limit, the generation of air bubbles and the like during melting of the methacrylic resin composition in the hot plate fusion method is likely to be effectively suppressed. When the MFR is at least the lower limit, the moldability of the methacrylic resin composition tends to be good.
- the methacrylic polymer in the present invention is a polymer whose main component is a repeating unit derived from methyl methacrylate (hereinafter also referred to as "methyl methacrylate unit").
- methyl methacrylate unit a repeating unit derived from methyl methacrylate
- the methacrylic resin composition of the present invention improves the transparency of the obtained resin molding, suppresses thermal decomposition of the resin molding, and improves weather resistance and moldability. can be made better.
- "mainly composed of methyl methacrylate units” means, as one aspect, that the content of methyl methacrylate units in the methacrylic polymer (100% by mass) is 70% by mass or more. .
- the content of methyl methacrylate units in the methacrylic polymer (100% by mass) is preferably 70% by mass or more.
- examples of such a methacrylic polymer include, for example, a homopolymer of methyl methacrylate, a repeating unit derived from a monomer other than methyl methacrylate with 70% by mass or more and less than 100% by mass of methyl methacrylate units (hereinafter referred to as "other (also referred to as "monomer unit").
- a monomer other than methyl methacrylate that forms another monomer unit is not particularly limited as long as it is a monomer that can be copolymerized with methyl methacrylate. It may be a monofunctional monomer having one radically polymerizable double bond in one molecule, or a polyfunctional monomer having two or more radically polymerizable double bonds in one molecule. may Acrylic acid esters are preferred from the viewpoint of an excellent balance between fluidity, moldability, and thermal decomposability of the methacrylic polymer.
- the methacrylic polymer contains a repeating unit derived from an acrylic acid ester as another monomer unit (hereinafter also referred to as "acrylic acid ester unit")
- the methacrylic polymer (100% by mass) contains methacrylic It is preferable to contain 70% by mass or more and less than 100% by mass of methyl acid units and 0% by mass or more and 30% by mass or less of acrylic acid ester units, and 80% by mass or more and 99.9% by mass or less of methyl methacrylate units and acrylic It is more preferable to contain 0.1% by mass or more and 20% by mass or less of acid ester units, and 90% by mass or more and 99.5% by mass or less of methyl methacrylate units and 0.5% by mass or more and 10% by mass of acrylic acid ester units. More preferably, it contains:
- acrylic esters examples include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate. Ethyl is preferred.
- Acrylic acid esters may be used alone or in combination of two or more.
- the main chain includes repeating units derived from (meth)acrylate monomers (hereinafter also referred to as "(meth)acrylate units”) and structures derived from ring structures.
- a polymer (A) containing a unit hereinafter abbreviated as "ring structure unit”.
- Ring structural units include, for example, glutaric anhydride structural units, maleic anhydride structural units, glutarimide structural units, lactone ring structural units, and N-substituted maleimide structural units.
- One type of ring structural unit may be used alone, or two or more types may be used in combination.
- the lower limit of the content of (meth)acrylate units in the polymer (A) is not particularly limited. From the viewpoint of not impairing the inherent performance of the acrylic resin, that is, the obtained resin molded article has excellent transparency, processability, and mechanical properties, the repeating unit (including the structural unit) contained in the polymer (A) is used. .) is preferably 80 mol %, more preferably 90 mol %, and even more preferably 94 mol %, relative to the total number of moles (100 mol %) of .
- the upper limit of the content of (meth)acrylate units in the polymer (A) is not particularly limited.
- the resin molding is preferably 99.999 mol%, more preferably 99.9 mol%, relative to the total number of moles (100 mol%) of the repeating units contained in the polymer (A). , 99.5 mol % is more preferred.
- the above upper limit and lower limit can be combined arbitrarily. For example, 80 to 99.999 mol% is preferred, 90 to 99.9 mol% is more preferred, and 94 to 99.5 mol% is even more preferred.
- the lower limit of the content of ring structural units in the polymer (A) is not particularly limited. From the viewpoint that the obtained resin molding has excellent heat resistance, it is preferably 0.001 mol %, more preferably 0.01 mol %, relative to the total number of moles (100 mol %) of the repeating units contained in the polymer (A). , 0.05 mol % is more preferred.
- the upper limit of the content ratio of the ring structural unit in the polymer (A) is not particularly limited.
- the obtained resin molding has excellent heat resistance, suppression of molding coloring, molding appearance, and excellent weather resistance, relative to the total number of moles (100 mol%) of the repeating units contained in the polymer (A), 10 mol % is preferred, 3 mol % is more preferred, and 0.3 mol % is even more preferred.
- the above upper limit and lower limit can be combined arbitrarily. For example, 0.001 to 10 mol% is preferred, 0.01 to 3 mol% is more preferred, and 0.05 to 0.3 mol% is even more preferred.
- Examples of the (meth)acrylic acid ester forming the (meth)acrylate unit include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n -butyl (meth)acrylate, iso-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate ) acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, norbornyl (meth)acrylate, adamantyl (meth)acrylate, di
- the (meth)acrylic acid ester unit can contain a structural unit derived from a monomer having a carboxyl group (hereinafter also referred to as a "monomer unit having a carboxyl group").
- a monomer unit having a part of carboxyl groups can form a ring structural unit through a cyclization reaction with an ester group, for example, and introduce the ring structural unit into the main chain of the methacrylic polymer. Therefore, the methacrylic polymer may contain a monomer unit having a carboxyl group.
- monomers having a carboxyl group include acrylic acid, methacrylic acid, 2-(hydroxymethyl)acrylic acid, 2-(hydroxyethyl)acrylic acid and crotonic acid.
- a monomer having a carboxyl group may be used alone or in combination of two or more.
- Unit (A1) a repeating unit (A1) derived from methyl methacrylate (hereinafter also referred to as “unit (A1)"), (meth)acrylic acid derived A repeating unit (A2) (hereinafter also referred to as “unit (A2)”), and a glutaric anhydride structural unit (A3) (hereinafter also referred to as “unit (A3)”) as a ring structural unit.
- unit (A3) is represented by the following chemical structural formula.
- RA and RB each independently represent a hydrogen atom or a methyl group.
- the lower limit of the content of the units (A1) in the polymer (A) is not particularly limited. From the viewpoint that the obtained resin molding does not impair the original performance of the acrylic resin, which is excellent in transparency, workability, and mechanical properties, the total number of moles of repeating units contained in the polymer (A) (100 mol% ), preferably 80 mol %, more preferably 90 mol %, and even more preferably 94 mol %.
- the upper limit of the content of the units (A1) in the polymer (A) is not particularly limited.
- the resulting resin molded product is preferably 99.4 mol%, more preferably 99 mol%, and 98 mol% with respect to the total number of moles (100 mol%) of the repeating units contained in the polymer (A). % is more preferred.
- the above upper limit and lower limit can be combined arbitrarily. For example, 80 to 99.4 mol% is preferred, 90 to 99 mol% is more preferred, and 94 to 98 mol% is even more preferred.
- Methacrylic acid is preferable as the unit (A2) because the heat resistance of the obtained resin molding is excellent.
- the lower limit of the content of the units (A2) in the polymer (A) is not particularly limited. From the viewpoint of excellent heat resistance and mechanical properties of the obtained resin molded product, it is preferably 0.5 mol%, more preferably 1 mol%, relative to the total number of moles (100 mol%) of the repeating units contained in the polymer (A). Preferably, 2 mol % is more preferable.
- the upper limit of the content of the units (A2) in the polymer (A) is not particularly limited.
- the total number of moles (100 mol%) of the repeating units contained in the polymer (A) On the other hand, 20 mol % is preferred, 7 mol % is more preferred, and 3.5 mol % is even more preferred.
- the above upper limit and lower limit can be combined arbitrarily. For example, 0.5 to 20 mol% is preferred, 1 to 7 mol% is more preferred, and 2 to 3.5 mol% is even more preferred.
- the lower limit of the content of the units (A3) in the polymer (A) is not particularly limited. From the viewpoint that the obtained resin molding has excellent heat resistance, it is preferably 0.001 mol %, more preferably 0.01 mol %, relative to the total number of moles (100 mol %) of the repeating units contained in the polymer (A). , 0.05 mol % is more preferred.
- the upper limit of the content of the unit (A3) in the polymer (A) is preferably 10 mol%, and 3 mol%, from the viewpoints of suppressing molding coloration of the obtained resin molding, molding appearance, and excellent weather resistance. More preferably, 0.3 mol % is even more preferable.
- the above upper limit and lower limit can be combined arbitrarily. For example, 0.001 to 10 mol% is preferred, 0.01 to 3 mol% is more preferred, and 0.05 to 0.3 mol% is even more preferred.
- the unit (A3) is a copolymer obtained by copolymerizing methyl methacrylate and (meth)acrylic acid, and a methoxycarbonyl group derived from the unit (A1) and a carboxyl group derived from the adjacent unit (A2). It may be a unit constructed by a cyclization reaction.
- the content of each unit in the polymer is a value calculated from 1 H-NMR measurement.
- the method disclosed in WO2019/013186 can be used.
- the method for producing a polymer containing units (A1), units (A2) and units (A3) is not particularly limited.
- the manufacturing methods disclosed in International Publication No. 2017/022393 and International Publication No. 2019/013186 can be used.
- the mass average molecular weight of the methacrylic polymer is not particularly limited. Preferably, it can be between 50,000 and 150,000, preferably between 70,000 and 130,000. When the mass-average molecular weight of the methacrylic polymer is at least the lower limit, the mechanical properties of the obtained resin molding are excellent. When the mass average molecular weight of the methacrylic polymer is equal to or less than the upper limit, the fluidity of the methacrylic resin composition for hot plate welding is excellent.
- the weight average molecular weight is a value measured by gel permeation chromatography using standard polystyrene as a standard sample. In order to control the weight average molecular weight of the methacrylic polymer, it is preferable to adjust the amount of the chain transfer agent in the polymerization of the monomer mixture.
- the method for producing the methacrylic polymer is not particularly limited. Examples thereof include bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. A bulk polymerization method and a suspension polymerization method are preferable from the viewpoint of excellent productivity.
- the fatty acid in the present invention makes it difficult for stringing to occur when the resin composition is separated from the hot plate during hot plate fusion, and also improves mold releasability during injection molding. It is a component that is added to make it difficult for the resin composition to leave a peeling residue. That is, the fatty acid in the present invention makes it difficult for the resin composition to string when the resin composition is separated from the hot plate during hot plate fusion, and furthermore, the resin composition has excellent releasability from the mold for injection molding. It is an ingredient for making things.
- Fatty acids include chain hydrocarbon compounds having at least one carboxyl group in the molecule.
- a chain hydrocarbon compound having at least one carboxyl group in the molecule means a compound in which the carbon atom to which the carboxyl group is bonded is a constituent atom of the carbon chain.
- the carbon chain in the chain hydrocarbon compound having at least one carboxyl group in the molecule may be saturated or unsaturated, and may be linear or branched. good too.
- a chain hydrocarbon compound having one carboxyl group is preferable as the fatty acid.
- the upper limit of the 10% weight loss temperature of fatty acids is not particularly limited. It is preferably 250° C. or lower, more preferably 240° C. or lower, more preferably 230° C. or lower, from the viewpoint of better releasability from the mold during injection molding and better hot plate fusion of the obtained resin molded product. More preferred.
- the 10% weight loss temperature is equal to or lower than the above upper limit, the fatty acid contained in the resin molded body is localized in the melted portion during hot plate fusion, making it difficult for stringing to occur.
- the fatty acid contained in the resin composition is easily volatilized in the mold, and as a result, the liquefied or condensed fatty acid adhering to the mold surface diffuses into the methacrylic resin composition injected into the mold later. , and migrating, the fatty acid is present at a high content on the surface and in the vicinity of the surface of the finally obtained resin molding.
- the lower limit of the 10% weight loss temperature of fatty acids is not particularly limited. It is preferably 150° C. or higher, more preferably 170° C. or higher, and 200° C. or higher from the viewpoint of better releasability from the mold during injection molding and better hot plate fusion of the obtained resin molded product. More preferred. If the 10% weight loss temperature is equal to or higher than the above lower limit, excessive volatilization of fatty acids from the resin molded article during hot plate fusion is suppressed, and deterioration of hot plate releasability is suppressed. During molding, the fatty acid volatilized in the mold adheres to the mold surface and tends to liquefy or condense. As a result, the amount of fatty acid discharged as gas from the gas vent of the mold is suppressed, It is presumed that this is because a high content of fatty acids can be present on the surface and in the vicinity of the surface of the molded resin article.
- the 10% weight loss temperature of fatty acids is preferably 150 to 250°C, more preferably 170 to 240°C, even more preferably 200 to 230°C.
- the lower limit of the melting point of fatty acids is not particularly limited.
- the temperature is preferably 50° C. or higher, more preferably 55° C. or higher, from the viewpoint of better releasability from the mold during injection molding and better hot-plate fusion bonding of the resulting resin molded product. 60° C. or higher is more preferable.
- the melting point of the fatty acid is at least the above lower limit, the decrease in the viscosity of the methacrylic resin composition during hot plate fusion can be suppressed, so stringing is less likely to occur, and the fatty acid contained in the methacrylic resin composition
- the resin is filled into the mold during injection molding, it becomes easier to diffuse in the molten resin. It is speculated that the condensed fatty acid diffuses and migrates, resulting in a high fatty acid content on the surface and in the vicinity of the surface of the finally obtained resin molding.
- the upper limit of the melting point of fatty acids is not particularly limited. From the viewpoint of better hot-plate fusion bondability of the obtained resin molding, the temperature is preferably 100° C. or lower, more preferably 90° C. or lower, and even more preferably 80° C. or lower.
- the melting point of the fatty acid is equal to or lower than the above upper limit, the effect of suppressing the stringing of the fatty acid in the resin molded product during hot plate fusion is easily obtained, and the fatty acid volatilized in the mold during injection molding is It is presumed that the fatty acid is liquefied or condensed on the mold surface to facilitate the formation of a film layer composed of fatty acids on the mold surface, and as a result, the above-described functions and effects can be easily obtained.
- the melting point of the fatty acid is preferably 50-100°C, more preferably 55-90°C, even more preferably 60-80°C.
- the molecular weight of fatty acids is not particularly limited. Fatty acids with a molecular weight of 100-500 can be used, with 200-400 being more preferred. When the molecular weight of the fatty acid is at least the above lower limit, the volatility of the fatty acid is low, and sufficient effects can be obtained for improving releasability from the mold during injection molding and hot plate fusion bonding. . If the molecular weight of the fatty acid is equal to or less than the above upper limit, the compatibility with the methacrylic polymer is high, so that it is easy to release from the mold during injection molding and stringing from the hot plate during hot plate fusion. Also, when the hot plate and mold are separated from the hot plate and the mold, less fatty acid remains on the surface of the hot plate and mold, so the surface of the hot plate and mold becomes dirty, and the obtained resin molding becomes cloudy. hard to do.
- the number of carbon atoms in fatty acids is not particularly limited. Preferably, it is 10-22. If the number of carbon atoms is at least the above lower limit, the volatility of the fatty acid is low, so that stringiness is less likely to occur when releasing from the mold during injection molding and when separating from the hot plate during hot plate fusion bonding. Prone.
- the compatibility with the methacrylic polymer is high, so the releasability from the mold and hot plate fusion are excellent, and when separating from the hot plate and the mold, Since the amount of fatty acid remaining on the surface of the hot plate and mold is reduced, the surface of the hot plate and mold is less likely to be stained, and the obtained resin molding is less likely to be cloudy.
- fatty acids examples include saturated fatty acids such as lauric acid, palmitic acid, stearic acid, myristic acid and behenic acid, and unsaturated fatty acids such as oleic acid and linoleic acid. is preferred.
- a fatty acid may be used individually by 1 type, and may use 2 or more types together.
- the content of fatty acid in the methacrylic resin composition of the present invention is not particularly limited. It can be 0.01 to 1 part by mass, more preferably 0.1 to 0.3 part by mass, with respect to 100 parts by mass of the methacrylic polymer.
- the fatty acid content is at least the above lower limit, releasability from molds during injection molding and hot-plate fusion bonding are likely to be improved. If it is less than the above upper limit, the amount of fatty acid remaining on the surface of the hot plate and the mold is reduced when the hot plate and the mold are separated, so the surface of the hot plate and the mold is dirty, and the obtained resin molded body is reduced. Cloudiness is less likely to occur.
- the content of fatty acids in the methacrylic resin composition of the present invention is not particularly limited. It can be 0.01 to 1% by mass, more preferably 0.1 to 0.3% by mass, relative to the total mass (100% by mass) of the methacrylic resin composition of the present invention.
- the fatty acid content is at least the above lower limit, the releasability from the mold during injection molding and the hot plate fusion bondability are likely to be improved. If it is less than the upper limit, the amount of fatty acid remaining on the surface of the hot plate and the mold is reduced when the hot plate and the mold are separated. Cloudiness is less likely to occur.
- the methacrylic resin composition of the present invention may contain other additives such as ultraviolet absorbers, light diffusing agents, antioxidants, and colorants within a range that does not affect the effects of the present invention. , pigments, dyes, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants, plasticizers and antistatic agents.
- additives such as ultraviolet absorbers, light diffusing agents, antioxidants, and colorants within a range that does not affect the effects of the present invention. , pigments, dyes, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants, plasticizers and antistatic agents.
- Examples of the method for producing the methacrylic resin composition of the present invention include the following methods (1) and (2).
- the methacrylic resin composition of the present invention is less likely to cause stringing when the resin composition is separated from the hot plate during hot plate fusion, and less likely to leave a peeling residue of the resin composition on the mold surface during injection molding. Therefore, a resin molded article obtained by injection molding the methacrylic resin composition of the present invention can be suitably used as a member for hot plate welding.
- the fusion bonding method of the present invention includes the steps of bringing at least part of a first member formed from the methacrylic resin composition of the present invention into contact with a hot plate to melt it, separating the first member from the hot plate, crimping with the second member.
- the material of the second member is not particularly limited as long as it is heat-sealable with the methacrylic polymer of the present invention. Examples include styrene-based resins such as ABS, SAN, AS, and MS resins, polycarbonate-based resins, and polyvinyl chloride-based resins.
- a member formed from the methacrylic resin composition of the present invention can also be used as the second member.
- FIG. 1 is a process diagram showing one embodiment of the fusion bonding method of the present invention.
- a hot plate 3 is placed between the first member 1 and the second member 2 (FIG. 1(a)), and at least a part of the first member 1 and the second member 2 is brought into contact with the hot plate 3. 1(b)), separated from the hot plate 4 (FIG. 1(c)), and melted portion 1a of the first member and melted portion 2a of the second member are fused together. (Crimping), the first member 1 and the second member 2 can be joined (FIG. 1(d)).
- a vehicle member of the present invention includes a composite member formed by bonding a first member and a second member.
- the first member in the vehicle member of the present invention contains a methacrylic polymer and a fatty acid.
- the first member in the vehicle member of the present invention may be a member formed from the methacrylic resin composition of the present invention.
- a composite member formed by bonding the first member and the second member may be formed by fusing the first member and the second member.
- the ejector pin pressure was measured by the following method.
- the pellet-shaped methacrylic resin compositions obtained in Examples and Comparative Examples were dried with hot air at 80 ° C. for about 16 hours, and then an injection molding machine (model name: EC75-SXII, Shibaura Kikai) set at a cylinder temperature of 260 ° C. (manufactured by Co., Ltd.), and a mold provided with a gas vent (75 mm in vertical diameter and 3 mm in thickness) (4) (Fig. 2) can be molded.
- Ejection pins for releasing the molded product are arranged one in the center part of the disk-shaped mold and four in the peripheral part of the mold at equal intervals. Continuous molding is performed under the conditions of a mold temperature of 90 ° C and an injection pressure of 80 MPa, and a pressure sensor installed on the back of the central ejector pin detects the ejector pin pressure ( Unit: MPa) was measured. The lower the ejector pin pressure value, the better the releasability.
- Hot plate adhesion As an index of hot plate fusion bondability, stringiness was observed by the following method. - Test piece preparation: The sprue portion (5) was cut from the disk-shaped molded product (4) (vertical diameter 75 mm, thickness 3 mm) molded for mold release evaluation, and a conical test piece (6) ( 10 mm in bottom diameter and 70 mm in height) were fabricated (see FIGS. 2 and 3). Hot plate: A plate made of SUS304 was placed on the hot plate (7), and this was used as the hot plate (8). The temperature of the hot plate surface was controlled by actually measuring the surface temperature of the hot plate (8) with a probe thermometer.
- ⁇ Test method After heating the surface temperature of the hot plate (8) to 260 ° C., the bottom part (9) (diameter 10 mm) of the conical test piece (6) is placed on the surface of the hot plate (8). After contacting for 20 seconds and melting the contact portion, the test piece (6) was pulled up to a height of 30 cm, and the presence or absence of stringing between the test piece (6) and the hot plate (8) was confirmed ( See Figure 4). Stringing is part of the thread-like methacrylic resin composition. Five test pieces were prepared, the above operation was performed once for each test piece, and evaluation was made according to the following criteria. (criterion) A: Stringing 0 times B: Stringing 1-2 times C: Stringing 3-5 times
- the melting points of fatty acids were evaluated by the following method using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., model: DSC-6200). About 10 mg of fatty acid is placed in an aluminum sample container, heated to 200° C. at a temperature increase rate of 10° C./min, held for 5 minutes to melt, and then cooled to 0° C. at 10° C./min. The temperature was again raised at a temperature elevation rate of 10°C/min, held for 5 minutes, and then lowered at 10°C/min.
- DSC differential scanning calorimeter
- the 10% weight loss temperature of fatty acids 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 raised from 40° C. to 500° C. at a heating rate of 10° C./min, and the temperature at which the weight reduction rate was 10% (10% by mass reduction) was measured.
- TGA thermogravimetric analyzer
- MMA Methyl methacrylate (trade name: Acryester (registered trademark) M, manufactured by Mitsubishi Chemical Corporation)
- MA Methyl acrylate (manufactured by Mitsubishi Chemical Corporation)
- MAA methacrylic acid polymerization initiator (1): 2,2'-azobis (2-methylpropionamidine) dihydrochloride polymerization initiator (2): 2,2'-azobis-2-methylbutyronitrile (trade name : V-59, manufactured by Wako Pure Chemical Industries, Ltd.)
- Polymer (2) Methacrylic polymer fatty acid compound (B-1) produced in Production Example 1: Myr
- the composition of the copolymer precursor (1) was analyzed according to the above-described measurement method for the "content of units (A), (B) and (C)", and found to be 96.0 mol% of MMA units and methacrylic acid. 3.0 mol % of repeating units (hereinafter referred to as "MAA units”) derived from methyl acrylate and 1.0 mol % of repeating units (hereinafter referred to as "MA units”) derived from methyl acrylate.
- the copolymer precursor (1) is supplied to a twin-screw extruder (model name “PCM30”, manufactured by Ikegai Co., Ltd.) and kneaded at 250° C. to obtain a pellet-shaped methacrylic polymer, which is then weighed. Combined (2).
- the composition of the obtained polymer (2) was 97.00 mol % of MMA units, 2.99 mol % of (meth)acrylic acid units, and 0.01 mol % of glutaric anhydride structural units.
- the (meth)acrylic acid units include MAA units and MA units.
- Example 1 100 parts by mass of polymer (1) and 0.1 part by mass of fatty acid compound (B-1) as fatty acid are supplied to a twin-screw extruder (model name “TEM35”, manufactured by Shibaura Machine Co., Ltd.), and the extruder Melt-kneading was carried out at a cylinder temperature of 250°C, and a pellet-shaped methacrylic resin composition was obtained at a mold temperature of 60°C. Table 1 shows the evaluation results of the obtained methacrylic resin composition.
- Examples 2-3, Comparative Examples 1-7 A methacrylic resin composition in the form of pellets was obtained in the same manner as in Example 1, except that the type of fatty acid compound was changed. Table 1 shows the evaluation results of the obtained methacrylic resin composition.
- Example 4 A methacrylic resin composition in the form of pellets was obtained in the same manner as in Example 1, except that the polymer (2) was used instead of the polymer (1) and the type and amount of the fatty acid compound added were changed. rice field. Table 1 shows the evaluation results of the obtained methacrylic resin composition.
- the resin moldings of Examples 1 to 4 were excellent in releasability during injection molding and hot plate fusion bonding. Since the resin molding of Reference Example 1 did not contain fatty acid, it was inferior in releasability during injection molding and hot plate fusion bonding. Although the resin moldings of Comparative Examples 1 to 9 contained a fatty acid compound, they were inferior in releasability during injection molding and hot plate fusion bonding since no fatty acid was used.
- the methacrylic resin composition for hot plate welding of the present invention is less likely to cause stringing when the resin composition is separated from the hot plate during hot plate welding, and has excellent hot plate welding properties.
- the resin composition is less likely to leave a peeling residue on the surface of the mold during injection molding, and is excellent in releasability from the mold. Therefore, the molded article containing the methacrylic resin composition for hot plate welding of the present invention can be used as a vehicle member such as a tail lamp cover, a head lamp cover, and a meter panel such as a vehicle interior and exterior material; a building member; It can be suitably used as a raw material for housing equipment members such as flush toilets, and is particularly suitable as a raw material for vehicle members.
- vehicle parts examples include tail lamp covers, head lamp covers, meter panels, door mirror housings, pillar covers (sash covers), license garnishes, front grills, fog garnishes, and emblems.
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Abstract
Provided is a methacrylic resin composition for hot-plate welding which, when separated from the hot plate in hot-plate welding, is less apt to string and which, when demolded in injection molding, is less apt to leave a residue on the mold surface, that is, which is suitable for injection molding and hot-plate welding. This methacrylic resin composition for hot-plate welding comprises a methacrylic polymer and a fatty acid.
Description
本発明は、熱板融着用メタクリル系樹脂組成物、熱板融着用メタクリル系樹脂組成物の熱板融着への使用、融着方法、及び車両用部材に関する。
本願は、２０２１年３月９日に日本出願された特願２０２１－０３６９１４号に基づき優先権を主張し、その内容をここに援用する。 TECHNICAL FIELD The present invention relates to a methacrylic resin composition for hot plate welding, use of the methacrylic resin composition for hot plate welding in hot plate welding, a welding method, and a vehicle member.
This application claims priority based on Japanese Patent Application No. 2021-036914 filed in Japan on March 9, 2021, the content of which is incorporated herein.
本願は、２０２１年３月９日に日本出願された特願２０２１－０３６９１４号に基づき優先権を主張し、その内容をここに援用する。 TECHNICAL FIELD The present invention relates to a methacrylic resin composition for hot plate welding, use of the methacrylic resin composition for hot plate welding in hot plate welding, a welding method, and a vehicle member.
This application claims priority based on Japanese Patent Application No. 2021-036914 filed in Japan on March 9, 2021, the content of which is incorporated herein.
メタクリル系樹脂は、その優れた外観、透明性、耐候性、耐薬品性等から、テールランプカバーや、ヘッドランプカバー、メーターパネルといった車両の内外装材料等の車両用部材；建築部材；洗面化粧台、浴槽、水洗便器等の住宅設備向け部材等、多くの用途に用いられている。
メタクリル系樹脂をこれらの用途に用いる場合、かかる部材は、ＭＳ樹脂やＡＢＳ樹脂等のようなスチレン系樹脂や、ポリカーボネート系樹脂等のメタクリル系樹脂以外の樹脂からなる部材と接合され、加工される。これらの部材を接合する方法として、熱板融着法が知られている（特許文献１～４）。
熱板融着法とは、各部材の接合面をそれぞれ金属製の熱板に密着させることにより加熱、溶融し、熱板を退避させた後、樹脂が冷えて固まるまでに、他の部材と溶着（圧着）して接合する方法であり、高い溶着強度が得られる。また、熱板融着法は、大きな部品のどうしを溶着することが可能であり、接着剤を塗布する手間や接着剤を硬化させる時間を省くことができる等の利点があることから、生産性に優れた方法である。 Due to its excellent appearance, transparency, weather resistance, chemical resistance, etc., methacrylic resins are used as vehicle parts such as tail lamp covers, head lamp covers, meter panels, and other vehicle interior and exterior materials; building materials; , bathtubs, flush toilets, and other housing equipment.
When a methacrylic resin is used for these purposes, such a member is joined with a member made of a styrene resin such as an MS resin or an ABS resin, or a resin other than a methacrylic resin such as a polycarbonate resin, and processed. . A hot plate fusion method is known as a method for joining these members (Patent Documents 1 to 4).
In the hot plate fusion method, each member is heated and melted by bringing the joint surface of each member into close contact with a metal hot plate. It is a method of joining by welding (crimping), and high welding strength can be obtained. In addition, the hot plate fusion method is capable of welding large parts together, and has the advantage of eliminating the time and effort required to apply adhesive and harden the adhesive. is an excellent method for
メタクリル系樹脂をこれらの用途に用いる場合、かかる部材は、ＭＳ樹脂やＡＢＳ樹脂等のようなスチレン系樹脂や、ポリカーボネート系樹脂等のメタクリル系樹脂以外の樹脂からなる部材と接合され、加工される。これらの部材を接合する方法として、熱板融着法が知られている（特許文献１～４）。
熱板融着法とは、各部材の接合面をそれぞれ金属製の熱板に密着させることにより加熱、溶融し、熱板を退避させた後、樹脂が冷えて固まるまでに、他の部材と溶着（圧着）して接合する方法であり、高い溶着強度が得られる。また、熱板融着法は、大きな部品のどうしを溶着することが可能であり、接着剤を塗布する手間や接着剤を硬化させる時間を省くことができる等の利点があることから、生産性に優れた方法である。 Due to its excellent appearance, transparency, weather resistance, chemical resistance, etc., methacrylic resins are used as vehicle parts such as tail lamp covers, head lamp covers, meter panels, and other vehicle interior and exterior materials; building materials; , bathtubs, flush toilets, and other housing equipment.
When a methacrylic resin is used for these purposes, such a member is joined with a member made of a styrene resin such as an MS resin or an ABS resin, or a resin other than a methacrylic resin such as a polycarbonate resin, and processed. . A hot plate fusion method is known as a method for joining these members (
In the hot plate fusion method, each member is heated and melted by bringing the joint surface of each member into close contact with a metal hot plate. It is a method of joining by welding (crimping), and high welding strength can be obtained. In addition, the hot plate fusion method is capable of welding large parts together, and has the advantage of eliminating the time and effort required to apply adhesive and harden the adhesive. is an excellent method for
熱板融着法では、熱板温度を高くすることで、各部材の接合部分を短時間で溶融させることができる。しかし、熱板温度が高すぎると、各部材を熱板から引き離す際に、樹脂の一部が熱板からうまくはがれず、糸状に引き伸ばされる現象（いわゆる糸曳き）が見られ、製品外観が損なわれてしまうことがある。
特許文献１～４に開示されているメタクリル系樹脂組成物は、熱板で溶融した後、熱板から引き離す際に、樹脂の一部が熱板からうまく剥離されず、糸曳きを生じたり、射出成形時に金型から成形体を引き離す際に、金型の表面に樹脂が残る現象（いわゆる剥離残渣）が見られたりすることがある。このような場合、部材の接合面が荒れてしまうことで製品外観が損なわれたり、熱板融着の熱板表面や、射出成形の金型表面の不要な洗浄作業が必要となったりするという課題があった。 In the hot plate fusion method, by increasing the temperature of the hot plate, it is possible to melt the joint portions of the respective members in a short time. However, if the hot plate temperature is too high, when the parts are separated from the hot plate, part of the resin cannot be peeled off from the hot plate and is stretched like a thread (so-called stringing), resulting in poor product appearance. It may get damaged.
In the methacrylic resin compositions disclosed inPatent Documents 1 to 4, after being melted on the hot plate, when the resin is pulled away from the hot plate, part of the resin is not successfully peeled off from the hot plate, causing stringiness. When the molded product is separated from the mold during injection molding, a phenomenon in which resin remains on the surface of the mold (so-called peeling residue) may be observed. In such cases, the surface of the parts to be joined becomes rough and the appearance of the product is damaged, and unnecessary cleaning of the surface of the hot plate for hot plate fusion and the surface of the mold for injection molding is required. I had a problem.
特許文献１～４に開示されているメタクリル系樹脂組成物は、熱板で溶融した後、熱板から引き離す際に、樹脂の一部が熱板からうまく剥離されず、糸曳きを生じたり、射出成形時に金型から成形体を引き離す際に、金型の表面に樹脂が残る現象（いわゆる剥離残渣）が見られたりすることがある。このような場合、部材の接合面が荒れてしまうことで製品外観が損なわれたり、熱板融着の熱板表面や、射出成形の金型表面の不要な洗浄作業が必要となったりするという課題があった。 In the hot plate fusion method, by increasing the temperature of the hot plate, it is possible to melt the joint portions of the respective members in a short time. However, if the hot plate temperature is too high, when the parts are separated from the hot plate, part of the resin cannot be peeled off from the hot plate and is stretched like a thread (so-called stringing), resulting in poor product appearance. It may get damaged.
In the methacrylic resin compositions disclosed in
本発明はこれらの問題点を解決することを目的とする。すなわち、本発明の目的は、熱板融着時に熱板から樹脂組成物を引き離す際に糸曳きを生じにくく、射出成形時に金型表面に樹脂組成物の剥離残渣が生じにくい、すなわち、射出成形と熱板融着に好適な、熱板融着用メタクリル系樹脂組成物を提供することにある。
The purpose of the present invention is to solve these problems. That is, the object of the present invention is to prevent stringing from occurring when the resin composition is separated from the hot plate during hot plate fusion, and to prevent the resin composition from leaving residue on the mold surface during injection molding. The object of the present invention is to provide a methacrylic resin composition for hot plate welding suitable for hot plate welding.
本発明者らは、前記課題を解決するため検討を重ねた結果、本発明に至った。すなわち、本発明は以下の態様を含む。
The present inventors have arrived at the present invention as a result of repeated studies to solve the above problems. That is, the present invention includes the following aspects.
［１］メタクリル系重合体及び脂肪酸を含む、熱板融着用メタクリル系樹脂組成物。
［２］前記脂肪酸の炭素数が１０～２２である、［１］の熱板融着用メタクリル系樹脂組成物。
［３］前記脂肪酸の１０％重量減少温度が２５０℃以下である、［１］又は［２］の熱板融着用メタクリル系樹脂組成物。
［４］前記脂肪酸の融点が５０℃以上である、［１］～［３］のいずれかの熱板融着用メタクリル系樹脂組成物。
［５］前記脂肪酸が分子内にカルボキシル基を少なくとも１個有する鎖状炭化水素化合物である、［１］～［４］のいずれかの熱板融着用メタクリル系樹脂組成物。
［６］前記脂肪酸の分子量が１００～５００である、［１］～［５］のいずれかの熱板融着用メタクリル系樹脂組成物。
［７］前記メタクリル系重合体１００質量部に対して、前記脂肪酸の含有量が０．０１～１質量部である、［１］～［６］のいずれかの熱板融着用メタクリル系樹脂組成物。
［８］熱板融着用メタクリル系樹脂組成物の総質量（１００質量％）に対して、前記脂肪酸の含有割合が０．０１～１質量％である、［１］～［６］のいずれかの熱板融着用メタクリル系樹脂組成物。
［９］前記脂肪酸が、ステアリン酸、パルミチン酸、及びミリスチン酸から選ばれる少なくとも１種を含む、［１］～［８］のいずれかの熱板融着用メタクリル系樹脂組成物。
［１０］前記メタクリル系重合体がメタクリル酸メチル由来の繰り返し単位を含み、前記メタクリル系重合体中の前記メタクリル酸メチル由来の繰り返し単位の含有割合が７０質量％以上である、［１］～［９］のいずれかの熱板融着用メタクリル系樹脂組成物。
［１１］前記メタクリル系重合体が、（メタ）アクリル酸エステル単量体由来の繰り返し単位及び環構造由来の構造単位を含む重合体（Ａ）であり、
前記環構造由来の構造単位が、グルタル酸無水物構造単位、マレイン酸無水物構造単位、グルタルイミド構造単位、ラクトン環構造単位、及びＮ－置換マレイミド構造単位から選ばれる少なくとも１種を含む、［１］～［１０］のいずれかの熱板融着用メタクリル系樹脂組成物。
［１２］前記重合体（Ａ）が、メタクリル酸メチル由来の繰り返し単位（Ａ１）、（メタ）アクリル酸由来の繰り返し単位（Ａ２）、及びグルタル酸無水物構造単位（Ａ３）を含む、［１１］の熱板融着用メタクリル系樹脂組成物。
［１３］車両用部材の原材料として用いる、［１］～［１２］のいずれかの熱板融着用メタクリル系樹脂組成物。
［１４］前記車両用部材が、テールランプカバー、ヘッドランプカバー、及びメーターパネルから選ばれる少なくとも１種である、［１３］の熱板融着用メタクリル系樹脂組成物。 [1] A methacrylic resin composition for hot plate welding, containing a methacrylic polymer and a fatty acid.
[2] The methacrylic resin composition for hot plate welding according to [1], wherein the fatty acid has 10 to 22 carbon atoms.
[3] The methacrylic resin composition for hot plate welding according to [1] or [2], wherein the fatty acid has a 10% weight loss temperature of 250° C. or lower.
[4] The methacrylic resin composition for hot plate welding according to any one of [1] to [3], wherein the fatty acid has a melting point of 50° C. or higher.
[5] The methacrylic resin composition for hot plate welding according to any one of [1] to [4], wherein the fatty acid is a chain hydrocarbon compound having at least one carboxyl group in the molecule.
[6] The methacrylic resin composition for hot plate welding according to any one of [1] to [5], wherein the fatty acid has a molecular weight of 100 to 500.
[7] The methacrylic resin composition for hot plate welding according to any one of [1] to [6], wherein the fatty acid content is 0.01 to 1 part by mass with respect to 100 parts by mass of the methacrylic polymer. thing.
[8] Any one of [1] to [6], wherein the content of the fatty acid is 0.01 to 1% by mass with respect to the total mass (100% by mass) of the methacrylic resin composition for hot plate welding. A methacrylic resin composition for hot plate welding.
[9] The methacrylic resin composition for hot plate welding according to any one of [1] to [8], wherein the fatty acid contains at least one selected from stearic acid, palmitic acid, and myristic acid.
[10] The methacrylic polymer contains a repeating unit derived from methyl methacrylate, and the content of the repeating unit derived from methyl methacrylate in the methacrylic polymer is 70% by mass or more, [1] to [ 9], the methacrylic resin composition for hot plate welding.
[11] The methacrylic polymer is a polymer (A) containing a repeating unit derived from a (meth)acrylate monomer and a structural unit derived from a ring structure,
The structural unit derived from the ring structure contains at least one selected from a glutaric anhydride structural unit, a maleic anhydride structural unit, a glutarimide structural unit, a lactone ring structural unit, and an N-substituted maleimide structural unit, [ The methacrylic resin composition for hot plate welding according to any one of 1] to [10].
[12] The polymer (A) comprises a repeating unit (A1) derived from methyl methacrylate, a repeating unit (A2) derived from (meth)acrylic acid, and a glutaric anhydride structural unit (A3), [11 ] methacrylic resin composition for hot plate welding.
[13] The methacrylic resin composition for hot plate welding according to any one of [1] to [12], which is used as a raw material for vehicle members.
[14] The methacrylic resin composition for hot plate welding according to [13], wherein the vehicle member is at least one selected from a tail lamp cover, a head lamp cover, and a meter panel.
［２］前記脂肪酸の炭素数が１０～２２である、［１］の熱板融着用メタクリル系樹脂組成物。
［３］前記脂肪酸の１０％重量減少温度が２５０℃以下である、［１］又は［２］の熱板融着用メタクリル系樹脂組成物。
［４］前記脂肪酸の融点が５０℃以上である、［１］～［３］のいずれかの熱板融着用メタクリル系樹脂組成物。
［５］前記脂肪酸が分子内にカルボキシル基を少なくとも１個有する鎖状炭化水素化合物である、［１］～［４］のいずれかの熱板融着用メタクリル系樹脂組成物。
［６］前記脂肪酸の分子量が１００～５００である、［１］～［５］のいずれかの熱板融着用メタクリル系樹脂組成物。
［７］前記メタクリル系重合体１００質量部に対して、前記脂肪酸の含有量が０．０１～１質量部である、［１］～［６］のいずれかの熱板融着用メタクリル系樹脂組成物。
［８］熱板融着用メタクリル系樹脂組成物の総質量（１００質量％）に対して、前記脂肪酸の含有割合が０．０１～１質量％である、［１］～［６］のいずれかの熱板融着用メタクリル系樹脂組成物。
［９］前記脂肪酸が、ステアリン酸、パルミチン酸、及びミリスチン酸から選ばれる少なくとも１種を含む、［１］～［８］のいずれかの熱板融着用メタクリル系樹脂組成物。
［１０］前記メタクリル系重合体がメタクリル酸メチル由来の繰り返し単位を含み、前記メタクリル系重合体中の前記メタクリル酸メチル由来の繰り返し単位の含有割合が７０質量％以上である、［１］～［９］のいずれかの熱板融着用メタクリル系樹脂組成物。
［１１］前記メタクリル系重合体が、（メタ）アクリル酸エステル単量体由来の繰り返し単位及び環構造由来の構造単位を含む重合体（Ａ）であり、
前記環構造由来の構造単位が、グルタル酸無水物構造単位、マレイン酸無水物構造単位、グルタルイミド構造単位、ラクトン環構造単位、及びＮ－置換マレイミド構造単位から選ばれる少なくとも１種を含む、［１］～［１０］のいずれかの熱板融着用メタクリル系樹脂組成物。
［１２］前記重合体（Ａ）が、メタクリル酸メチル由来の繰り返し単位（Ａ１）、（メタ）アクリル酸由来の繰り返し単位（Ａ２）、及びグルタル酸無水物構造単位（Ａ３）を含む、［１１］の熱板融着用メタクリル系樹脂組成物。
［１３］車両用部材の原材料として用いる、［１］～［１２］のいずれかの熱板融着用メタクリル系樹脂組成物。
［１４］前記車両用部材が、テールランプカバー、ヘッドランプカバー、及びメーターパネルから選ばれる少なくとも１種である、［１３］の熱板融着用メタクリル系樹脂組成物。 [1] A methacrylic resin composition for hot plate welding, containing a methacrylic polymer and a fatty acid.
[2] The methacrylic resin composition for hot plate welding according to [1], wherein the fatty acid has 10 to 22 carbon atoms.
[3] The methacrylic resin composition for hot plate welding according to [1] or [2], wherein the fatty acid has a 10% weight loss temperature of 250° C. or lower.
[4] The methacrylic resin composition for hot plate welding according to any one of [1] to [3], wherein the fatty acid has a melting point of 50° C. or higher.
[5] The methacrylic resin composition for hot plate welding according to any one of [1] to [4], wherein the fatty acid is a chain hydrocarbon compound having at least one carboxyl group in the molecule.
[6] The methacrylic resin composition for hot plate welding according to any one of [1] to [5], wherein the fatty acid has a molecular weight of 100 to 500.
[7] The methacrylic resin composition for hot plate welding according to any one of [1] to [6], wherein the fatty acid content is 0.01 to 1 part by mass with respect to 100 parts by mass of the methacrylic polymer. thing.
[8] Any one of [1] to [6], wherein the content of the fatty acid is 0.01 to 1% by mass with respect to the total mass (100% by mass) of the methacrylic resin composition for hot plate welding. A methacrylic resin composition for hot plate welding.
[9] The methacrylic resin composition for hot plate welding according to any one of [1] to [8], wherein the fatty acid contains at least one selected from stearic acid, palmitic acid, and myristic acid.
[10] The methacrylic polymer contains a repeating unit derived from methyl methacrylate, and the content of the repeating unit derived from methyl methacrylate in the methacrylic polymer is 70% by mass or more, [1] to [ 9], the methacrylic resin composition for hot plate welding.
[11] The methacrylic polymer is a polymer (A) containing a repeating unit derived from a (meth)acrylate monomer and a structural unit derived from a ring structure,
The structural unit derived from the ring structure contains at least one selected from a glutaric anhydride structural unit, a maleic anhydride structural unit, a glutarimide structural unit, a lactone ring structural unit, and an N-substituted maleimide structural unit, [ The methacrylic resin composition for hot plate welding according to any one of 1] to [10].
[12] The polymer (A) comprises a repeating unit (A1) derived from methyl methacrylate, a repeating unit (A2) derived from (meth)acrylic acid, and a glutaric anhydride structural unit (A3), [11 ] methacrylic resin composition for hot plate welding.
[13] The methacrylic resin composition for hot plate welding according to any one of [1] to [12], which is used as a raw material for vehicle members.
[14] The methacrylic resin composition for hot plate welding according to [13], wherein the vehicle member is at least one selected from a tail lamp cover, a head lamp cover, and a meter panel.
［１５］［１］～［１４］のいずれかの熱板融着用メタクリル系樹脂組成物の熱板融着への使用。
[15] Use of the methacrylic resin composition for hot plate welding according to any one of [1] to [14] for hot plate welding.
［１６］［１］～［１４］のいずれかの熱板融着用メタクリル系樹脂組成物から形成された第１の部材の少なくとも一部を熱板に接触させて溶融させる工程と、
前記第１の部材を前記熱板から引き離し、第２の部材と圧着する工程と、を備える、第１の部材と第２の部材の融着方法。 [16] A step of bringing at least part of the first member formed from the methacrylic resin composition for hot plate welding according to any one of [1] to [14] into contact with a hot plate to melt;
pulling the first member away from the hot plate and crimping the first member to a second member.
前記第１の部材を前記熱板から引き離し、第２の部材と圧着する工程と、を備える、第１の部材と第２の部材の融着方法。 [16] A step of bringing at least part of the first member formed from the methacrylic resin composition for hot plate welding according to any one of [1] to [14] into contact with a hot plate to melt;
pulling the first member away from the hot plate and crimping the first member to a second member.
［１７］第１の部材と第２の部材とを接着してなる複合部材を含む車両用部材であって、
前記第１の部材が、メタクリル系重合体及び脂肪酸を含む、車両用部材。
［１８］第１の部材と第２の部材とを接着してなる複合部材を含む車両用部材であって、
前記第１の部材が、［１］～［１４］のいずれかの熱板融着用メタクリル系樹脂組成物から形成された部材である、車両用部材。 [17] A vehicle member including a composite member formed by bonding a first member and a second member,
A vehicle member, wherein the first member contains a methacrylic polymer and a fatty acid.
[18] A vehicle member including a composite member formed by bonding a first member and a second member,
A vehicle member, wherein the first member is a member formed from the methacrylic resin composition for hot plate welding according to any one of [1] to [14].
前記第１の部材が、メタクリル系重合体及び脂肪酸を含む、車両用部材。
［１８］第１の部材と第２の部材とを接着してなる複合部材を含む車両用部材であって、
前記第１の部材が、［１］～［１４］のいずれかの熱板融着用メタクリル系樹脂組成物から形成された部材である、車両用部材。 [17] A vehicle member including a composite member formed by bonding a first member and a second member,
A vehicle member, wherein the first member contains a methacrylic polymer and a fatty acid.
[18] A vehicle member including a composite member formed by bonding a first member and a second member,
A vehicle member, wherein the first member is a member formed from the methacrylic resin composition for hot plate welding according to any one of [1] to [14].
本発明によれば、熱板融着時に熱板から樹脂組成物を引き離す際に糸曳きを生じにくく、また、射出成形時に金型表面に樹脂組成物の剥離残渣が生じにくい、すなわち、射出成形と熱板融着に好適な、熱板融着用メタクリル系樹脂組成物を提供することができる。
According to the present invention, stringing is less likely to occur when the resin composition is separated from the hot plate during hot plate fusion, and peeling residue of the resin composition is less likely to occur on the mold surface during injection molding. It is possible to provide a methacrylic resin composition for hot plate welding suitable for hot plate welding.
本発明において、「（メタ）アクリレート」は、「アクリレート」及び「メタクリレート」から選ばれる少なくとも１種を意味し、「（メタ）アクリル酸」は、「アクリル酸」及び「メタクリル酸」から選ばれる少なくとも１種を意味する。
本発明において、「単量体」は未重合の化合物を意味し、「繰り返し単位」は単量体が重合することによって形成された単量体に由来する単位を意味する。繰り返し単位は、重合反応によって直接形成された単位であってもよく、ポリマーを処理することによって単位の一部が別の構造に変換されたものであってもよい。
本発明において、「質量％」は全体量１００質量％中に含まれる所定の成分の含有割合を示す。
本発明において、「得られた樹脂成形体」は、熱板融着用メタクリル系樹脂組成物を成形してなる成形体を意味する。
本発明において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。 In the present invention, "(meth)acrylate" means at least one selected from "acrylate" and "methacrylate", and "(meth)acrylic acid" is selected from "acrylic acid" and "methacrylic acid". means at least one.
In the present invention, "monomer" means an unpolymerized compound, and "repeating unit" means a unit derived from a monomer formed by polymerizing the monomer. The repeating unit may be a unit directly formed by a polymerization reaction, or may be a part of the unit converted to another structure by treating the polymer.
In the present invention, "% by mass" indicates the content ratio of a given component contained in 100% by mass of the total amount.
In the present invention, the "obtained resin molded article" means a molded article obtained by molding a methacrylic resin composition for hot plate welding.
In the present invention, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
本発明において、「単量体」は未重合の化合物を意味し、「繰り返し単位」は単量体が重合することによって形成された単量体に由来する単位を意味する。繰り返し単位は、重合反応によって直接形成された単位であってもよく、ポリマーを処理することによって単位の一部が別の構造に変換されたものであってもよい。
本発明において、「質量％」は全体量１００質量％中に含まれる所定の成分の含有割合を示す。
本発明において、「得られた樹脂成形体」は、熱板融着用メタクリル系樹脂組成物を成形してなる成形体を意味する。
本発明において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。 In the present invention, "(meth)acrylate" means at least one selected from "acrylate" and "methacrylate", and "(meth)acrylic acid" is selected from "acrylic acid" and "methacrylic acid". means at least one.
In the present invention, "monomer" means an unpolymerized compound, and "repeating unit" means a unit derived from a monomer formed by polymerizing the monomer. The repeating unit may be a unit directly formed by a polymerization reaction, or may be a part of the unit converted to another structure by treating the polymer.
In the present invention, "% by mass" indicates the content ratio of a given component contained in 100% by mass of the total amount.
In the present invention, the "obtained resin molded article" means a molded article obtained by molding a methacrylic resin composition for hot plate welding.
In the present invention, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
＜熱板融着用メタクリル系樹脂組成物＞
本発明の熱板融着用メタクリル系樹脂組成物（以下、適宜「メタクリル系樹脂組成物」という。）は、メタクリル系重合体及び脂肪酸を含む。 <Methacrylic resin composition for hot plate fusion>
The methacrylic resin composition for hot plate welding of the present invention (hereinafter referred to as "methacrylic resin composition" as appropriate) contains a methacrylic polymer and a fatty acid.
本発明の熱板融着用メタクリル系樹脂組成物（以下、適宜「メタクリル系樹脂組成物」という。）は、メタクリル系重合体及び脂肪酸を含む。 <Methacrylic resin composition for hot plate fusion>
The methacrylic resin composition for hot plate welding of the present invention (hereinafter referred to as "methacrylic resin composition" as appropriate) contains a methacrylic polymer and a fatty acid.
本発明のメタクリル系樹脂組成物のメルトフローレート（ＭＦＲ）は特に限定されない。好ましくは、ＩＳＯ １１３３－１：２０１１に準じ、温度２３０℃、荷重３．８ｋｇの条件で測定したＭＦＲが、０．１～１０ｇ／１０ｍｉｎであることが好ましく、０．２～５ｇ／１０ｍｉｎがより好ましく、０．３～２ｇ／１０ｍｉｎがさらに好ましい。
ＭＦＲが前記上限値以下であることより、熱板融着法におけるメタクリル系樹脂組成物の溶融時に気泡等の発生が効果的に抑制されやすい。ＭＦＲが前記下限値以上であることにより、メタクリル系樹脂組成物の成形性が良好となりやすい。 The melt flow rate (MFR) of the methacrylic resin composition of the present invention is not particularly limited. Preferably, according to ISO 1133-1: 2011, the MFR measured at a temperature of 230 ° C. and a load of 3.8 kg is preferably 0.1 to 10 g / 10 min, more preferably 0.2 to 5 g / 10 min. Preferably, 0.3 to 2 g/10 min is more preferable.
Since the MFR is equal to or less than the above upper limit, the generation of air bubbles and the like during melting of the methacrylic resin composition in the hot plate fusion method is likely to be effectively suppressed. When the MFR is at least the lower limit, the moldability of the methacrylic resin composition tends to be good.
ＭＦＲが前記上限値以下であることより、熱板融着法におけるメタクリル系樹脂組成物の溶融時に気泡等の発生が効果的に抑制されやすい。ＭＦＲが前記下限値以上であることにより、メタクリル系樹脂組成物の成形性が良好となりやすい。 The melt flow rate (MFR) of the methacrylic resin composition of the present invention is not particularly limited. Preferably, according to ISO 1133-1: 2011, the MFR measured at a temperature of 230 ° C. and a load of 3.8 kg is preferably 0.1 to 10 g / 10 min, more preferably 0.2 to 5 g / 10 min. Preferably, 0.3 to 2 g/10 min is more preferable.
Since the MFR is equal to or less than the above upper limit, the generation of air bubbles and the like during melting of the methacrylic resin composition in the hot plate fusion method is likely to be effectively suppressed. When the MFR is at least the lower limit, the moldability of the methacrylic resin composition tends to be good.
ＭＦＲを０．１～１０ｇ／１０ｍｉｎに制御するために、例えば、単量体単位の組成比の制御、メタクリル系重合体の質量平均分子量の調整を行うことができる。
In order to control the MFR to 0.1 to 10 g/10 min, for example, it is possible to control the composition ratio of the monomer units and adjust the weight average molecular weight of the methacrylic polymer.
＜メタクリル系重合体＞
本発明におけるメタクリル系重合体は、メタクリル酸メチル由来の繰り返し単位（以下、「メタクリル酸メチル単位」ともいう。）を主成分とする重合体である。
本発明のメタクリル系樹脂組成物は、メタクリル系重合体を含有することにより、得られた樹脂成形体の透明性が向上するとともに、樹脂成形体の熱分解が抑制され、耐候性、成形性を良好にすることができる。
本発明において、「メタクリル酸メチル単位を主成分とする」とは、一態様として、メタクリル系重合体（１００質量％）中のメタクリル酸メチル単位の含有割合が７０質量％以上であることをいう。 <Methacrylic polymer>
The methacrylic polymer in the present invention is a polymer whose main component is a repeating unit derived from methyl methacrylate (hereinafter also referred to as "methyl methacrylate unit").
By containing a methacrylic polymer, the methacrylic resin composition of the present invention improves the transparency of the obtained resin molding, suppresses thermal decomposition of the resin molding, and improves weather resistance and moldability. can be made better.
In the present invention, "mainly composed of methyl methacrylate units" means, as one aspect, that the content of methyl methacrylate units in the methacrylic polymer (100% by mass) is 70% by mass or more. .
本発明におけるメタクリル系重合体は、メタクリル酸メチル由来の繰り返し単位（以下、「メタクリル酸メチル単位」ともいう。）を主成分とする重合体である。
本発明のメタクリル系樹脂組成物は、メタクリル系重合体を含有することにより、得られた樹脂成形体の透明性が向上するとともに、樹脂成形体の熱分解が抑制され、耐候性、成形性を良好にすることができる。
本発明において、「メタクリル酸メチル単位を主成分とする」とは、一態様として、メタクリル系重合体（１００質量％）中のメタクリル酸メチル単位の含有割合が７０質量％以上であることをいう。 <Methacrylic polymer>
The methacrylic polymer in the present invention is a polymer whose main component is a repeating unit derived from methyl methacrylate (hereinafter also referred to as "methyl methacrylate unit").
By containing a methacrylic polymer, the methacrylic resin composition of the present invention improves the transparency of the obtained resin molding, suppresses thermal decomposition of the resin molding, and improves weather resistance and moldability. can be made better.
In the present invention, "mainly composed of methyl methacrylate units" means, as one aspect, that the content of methyl methacrylate units in the methacrylic polymer (100% by mass) is 70% by mass or more. .
メタクリル系重合体としては、メタクリル系重合体（１００質量％）中のメタクリル酸メチル単位の含有割合が、７０質量％以上であることが好ましい。このようなメタクリル系重合体として、例えば、メタクリル酸メチルの単独重合体、メタクリル酸メチル単位７０質量％以上１００質量％未満とメタクリル酸メチル以外の単量体由来の繰り返し単位（以下、「他の単量体単位」ともいう。）０質量％を超えて３０質量％以下とを含む共重合体を挙げることができる。
As for the methacrylic polymer, the content of methyl methacrylate units in the methacrylic polymer (100% by mass) is preferably 70% by mass or more. Examples of such a methacrylic polymer include, for example, a homopolymer of methyl methacrylate, a repeating unit derived from a monomer other than methyl methacrylate with 70% by mass or more and less than 100% by mass of methyl methacrylate units (hereinafter referred to as "other (also referred to as "monomer unit").
他の単量体単位を形成するメタクリル酸メチル以外の単量体としては、メタクリル酸メチルと共重合可能な単量体であれば特に限定されない。一分子内にラジカル重合可能な二重結合を１つ有する単官能単量体であってもよいし、一分子内にラジカル重合可能な二重結合を２つ以上有する多官能単量体であってもよい。メタクリル系重合体の流動性、成形性、及び熱分解性のバランスに優れる観点から、アクリル酸エステルが好ましい。
A monomer other than methyl methacrylate that forms another monomer unit is not particularly limited as long as it is a monomer that can be copolymerized with methyl methacrylate. It may be a monofunctional monomer having one radically polymerizable double bond in one molecule, or a polyfunctional monomer having two or more radically polymerizable double bonds in one molecule. may Acrylic acid esters are preferred from the viewpoint of an excellent balance between fluidity, moldability, and thermal decomposability of the methacrylic polymer.
メタクリル系重合体が、他の単量体単位としてアクリル酸エステル由来の繰り返し単位（以下、「アクリル酸エステル単位」ともいう。）を含む場合、メタクリル系重合体（１００質量％）中に、メタクリル酸メチル単位７０質量％以上１００質量％未満とアクリル酸エステル単位０質量％を超えて３０質量％以下とを含有することが好ましく、メタクリル酸メチル単位８０質量％以上９９．９質量％以下とアクリル酸エステル単位０．１質量％以上２０質量％以下とを含有することがより好ましく、メタクリル酸メチル単位９０質量％以上９９．５質量％以下とアクリル酸エステル単位０．５質量％以上１０質量％以下を含有することがさらに好ましい。
When the methacrylic polymer contains a repeating unit derived from an acrylic acid ester as another monomer unit (hereinafter also referred to as "acrylic acid ester unit"), the methacrylic polymer (100% by mass) contains methacrylic It is preferable to contain 70% by mass or more and less than 100% by mass of methyl acid units and 0% by mass or more and 30% by mass or less of acrylic acid ester units, and 80% by mass or more and 99.9% by mass or less of methyl methacrylate units and acrylic It is more preferable to contain 0.1% by mass or more and 20% by mass or less of acid ester units, and 90% by mass or more and 99.5% by mass or less of methyl methacrylate units and 0.5% by mass or more and 10% by mass of acrylic acid ester units. More preferably, it contains:
アクリル酸エステルとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸シクロヘキシル、アクリル酸ベンジル、アクリル酸２－エチルヘキシル、アクリル酸２－ヒドロキシエチルが挙げられ、アクリル酸メチル、アクリル酸エチルが好ましい。
アクリル酸エステルは、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate. Ethyl is preferred.
Acrylic acid esters may be used alone or in combination of two or more.
アクリル酸エステルは、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate. Ethyl is preferred.
Acrylic acid esters may be used alone or in combination of two or more.
メタクリル系重合体の別の態様としては、主鎖に、（メタ）アクリル酸エステル単量体由来の繰り返し単位（以下、「（メタ）アクリル酸エステル単位」ともいう。）及び環構造由来の構造単位（以下、「環構造単位」と略する。）を含む重合体（Ａ）を挙げることができる。環構造単位としては、例えば、グルタル酸無水物構造単位、マレイン酸無水物構造単位、グルタルイミド構造単位、ラクトン環構造単位、及びＮ－置換マレイミド構造単位が挙げられる。
環構造単位は、１種を単独で用いてもよく、２種以上を併用してもよい。 In another embodiment of the methacrylic polymer, the main chain includes repeating units derived from (meth)acrylate monomers (hereinafter also referred to as "(meth)acrylate units") and structures derived from ring structures. A polymer (A) containing a unit (hereinafter abbreviated as "ring structure unit") can be mentioned. Ring structural units include, for example, glutaric anhydride structural units, maleic anhydride structural units, glutarimide structural units, lactone ring structural units, and N-substituted maleimide structural units.
One type of ring structural unit may be used alone, or two or more types may be used in combination.
環構造単位は、１種を単独で用いてもよく、２種以上を併用してもよい。 In another embodiment of the methacrylic polymer, the main chain includes repeating units derived from (meth)acrylate monomers (hereinafter also referred to as "(meth)acrylate units") and structures derived from ring structures. A polymer (A) containing a unit (hereinafter abbreviated as "ring structure unit") can be mentioned. Ring structural units include, for example, glutaric anhydride structural units, maleic anhydride structural units, glutarimide structural units, lactone ring structural units, and N-substituted maleimide structural units.
One type of ring structural unit may be used alone, or two or more types may be used in combination.
重合体（Ａ）中の（メタ）アクリル酸エステル単位の含有割合の下限値は特に限定されない。得られた樹脂成形体が透明性に優れ、加工性、機械的特性に優れるというアクリル樹脂本来の性能を損なわない観点から、重合体（Ａ）に含まれる繰り返し単位（構造単位を含む。以下同様。）の総モル数（１００ｍｏｌ％）に対して、８０ｍｏｌ％が好ましく、９０ｍｏｌ％がより好ましく、９４ｍｏｌ％がさらに好ましい。重合体（Ａ）中の（メタ）アクリル酸エステル単位の含有割合の上限値は特に限定されない。得られた樹脂成形体の耐熱性に優れる観点から、重合体（Ａ）に含まれる繰り返し単位の総モル数（１００ｍｏｌ％）に対して、９９．９９９ｍｏｌ％が好ましく、９９．９ｍｏｌ％がより好ましく、９９．５ｍｏｌ％がさらに好ましい。上記の上限値及び下限値は任意に組み合わせることができる。例えば、８０～９９．９９９ｍｏｌ％が好ましく、９０～９９．９ｍｏｌ％がより好ましく、９４～９９．５ｍｏｌ％がさらに好ましい。
The lower limit of the content of (meth)acrylate units in the polymer (A) is not particularly limited. From the viewpoint of not impairing the inherent performance of the acrylic resin, that is, the obtained resin molded article has excellent transparency, processability, and mechanical properties, the repeating unit (including the structural unit) contained in the polymer (A) is used. .) is preferably 80 mol %, more preferably 90 mol %, and even more preferably 94 mol %, relative to the total number of moles (100 mol %) of . The upper limit of the content of (meth)acrylate units in the polymer (A) is not particularly limited. From the viewpoint of excellent heat resistance of the obtained resin molding, it is preferably 99.999 mol%, more preferably 99.9 mol%, relative to the total number of moles (100 mol%) of the repeating units contained in the polymer (A). , 99.5 mol % is more preferred. The above upper limit and lower limit can be combined arbitrarily. For example, 80 to 99.999 mol% is preferred, 90 to 99.9 mol% is more preferred, and 94 to 99.5 mol% is even more preferred.
重合体（Ａ）中の環構造単位の含有割合の下限値は特に限定されない。得られた樹脂成形体が耐熱性に優れる観点から、重合体（Ａ）に含まれる繰り返し単位の総モル数（１００ｍｏｌ％）に対して、０．００１ｍｏｌ％が好ましく、０．０１ｍｏｌ％がより好ましく、０．０５ｍｏｌ％がさらに好ましい。重合体（Ａ）中の環構造単位の含有割合の上限値は特に限定されない。得られた樹脂成形体が耐熱性に優れ、成形着色の抑制、成形外観、及び耐候性に優れる観点から、重合体（Ａ）に含まれる繰り返し単位の総モル数（１００ｍｏｌ％）に対して、１０ｍｏｌ％が好ましく、３ｍｏｌ％がより好ましく、０．３ｍｏｌ％がさらに好ましい。上記の上限値及び下限値は任意に組み合わせることができる。例えば、０．００１～１０ｍｏｌ％が好ましく、０．０１～３ｍｏｌ％がより好ましく、０．０５～０．３ｍｏｌ％がさらに好ましい。
The lower limit of the content of ring structural units in the polymer (A) is not particularly limited. From the viewpoint that the obtained resin molding has excellent heat resistance, it is preferably 0.001 mol %, more preferably 0.01 mol %, relative to the total number of moles (100 mol %) of the repeating units contained in the polymer (A). , 0.05 mol % is more preferred. The upper limit of the content ratio of the ring structural unit in the polymer (A) is not particularly limited. From the viewpoint that the obtained resin molding has excellent heat resistance, suppression of molding coloring, molding appearance, and excellent weather resistance, relative to the total number of moles (100 mol%) of the repeating units contained in the polymer (A), 10 mol % is preferred, 3 mol % is more preferred, and 0.3 mol % is even more preferred. The above upper limit and lower limit can be combined arbitrarily. For example, 0.001 to 10 mol% is preferred, 0.01 to 3 mol% is more preferred, and 0.05 to 0.3 mol% is even more preferred.
（メタ）アクリル酸エステル単位を形成する（メタ）アクリル酸エステルとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉｓｏ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉｓｏ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、グリシジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等の（メタ）アクリレート化合物；（メタ）アクリル酸等のカルボキシル基を有する化合物；を挙げることができ、得られた樹脂成形体の熱安定性が向上する観点から、メタクリル酸メチルが好ましい。
（メタ）アクリル酸エステルは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the (meth)acrylic acid ester forming the (meth)acrylate unit include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n -butyl (meth)acrylate, iso-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate ) 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 (meth) acrylate, 2-hydroxypropyl (meth) acrylate (meth) acrylate compounds; (meth) compounds having a carboxyl group such as acrylic acid; Methyl methacrylate is preferable from the viewpoint of improving the thermal stability of the obtained resin molding.
(Meth)acrylic acid esters may be used alone or in combination of two or more.
（メタ）アクリル酸エステルは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the (meth)acrylic acid ester forming the (meth)acrylate unit include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n -butyl (meth)acrylate, iso-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate ) 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 (meth) acrylate, 2-hydroxypropyl (meth) acrylate (meth) acrylate compounds; (meth) compounds having a carboxyl group such as acrylic acid; Methyl methacrylate is preferable from the viewpoint of improving the thermal stability of the obtained resin molding.
(Meth)acrylic acid esters may be used alone or in combination of two or more.
（メタ）アクリル酸エステル単位は、カルボキシル基を有する単量体に由来する構成単位（以下、「カルボキシル基を有する単量体単位」ともいう。）を含むことができる。一部のカルボキシル基を有する単量体単位は、例えばエステル基との間の環化反応により環構造単位を形成し、メタクリル系重合体の主鎖中に環構造単位を導入しうる。そのため、メタクリル系重合体に、カルボキシル基を有する単量体単位が含まれていてもよい。
カルボキシル基を有する単量体としては、例えば、アクリル酸、メタクリル酸、２－（ヒドロキシメチル）アクリル酸、２－（ヒドロキシエチル）アクリル酸、クロトン酸が挙げられる。
カルボキシル基を有する単量体は、１種を単独で用いてもよく、２種以上を併用してもよい。 The (meth)acrylic acid ester unit can contain a structural unit derived from a monomer having a carboxyl group (hereinafter also referred to as a "monomer unit having a carboxyl group"). A monomer unit having a part of carboxyl groups can form a ring structural unit through a cyclization reaction with an ester group, for example, and introduce the ring structural unit into the main chain of the methacrylic polymer. Therefore, the methacrylic polymer may contain a monomer unit having a carboxyl group.
Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, 2-(hydroxymethyl)acrylic acid, 2-(hydroxyethyl)acrylic acid and crotonic acid.
A monomer having a carboxyl group may be used alone or in combination of two or more.
カルボキシル基を有する単量体としては、例えば、アクリル酸、メタクリル酸、２－（ヒドロキシメチル）アクリル酸、２－（ヒドロキシエチル）アクリル酸、クロトン酸が挙げられる。
カルボキシル基を有する単量体は、１種を単独で用いてもよく、２種以上を併用してもよい。 The (meth)acrylic acid ester unit can contain a structural unit derived from a monomer having a carboxyl group (hereinafter also referred to as a "monomer unit having a carboxyl group"). A monomer unit having a part of carboxyl groups can form a ring structural unit through a cyclization reaction with an ester group, for example, and introduce the ring structural unit into the main chain of the methacrylic polymer. Therefore, the methacrylic polymer may contain a monomer unit having a carboxyl group.
Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, 2-(hydroxymethyl)acrylic acid, 2-(hydroxyethyl)acrylic acid and crotonic acid.
A monomer having a carboxyl group may be used alone or in combination of two or more.
重合体（Ａ）の一態様としては、（メタ）アクリル酸エステル単位として、メタクリル酸メチル由来の繰り返し単位（Ａ１）（以下、「単位（Ａ１）」ともいう。）、（メタ）アクリル酸由来の繰り返し単位（Ａ２）（以下、「単位（Ａ２）」ともいう。）、及び環構造単位としてグルタル酸無水物構造単位（Ａ３）（以下、「単位（Ａ３）」ともいう。）を含む重合体が挙げられる。
重合体（Ａ）が単位（Ａ３）を含むことにより、得られた樹脂成形体の耐熱性を向上させやすい。単位（Ａ３）は、以下の化学構造式で示される。 As one aspect of the polymer (A), as the (meth)acrylic acid ester unit, a repeating unit (A1) derived from methyl methacrylate (hereinafter also referred to as "unit (A1)"), (meth)acrylic acid derived A repeating unit (A2) (hereinafter also referred to as “unit (A2)”), and a glutaric anhydride structural unit (A3) (hereinafter also referred to as “unit (A3)”) as a ring structural unit. coalescence is mentioned.
By including the unit (A3) in the polymer (A), it is easy to improve the heat resistance of the obtained resin molding. Unit (A3) is represented by the following chemical structural formula.
重合体（Ａ）が単位（Ａ３）を含むことにより、得られた樹脂成形体の耐熱性を向上させやすい。単位（Ａ３）は、以下の化学構造式で示される。 As one aspect of the polymer (A), as the (meth)acrylic acid ester unit, a repeating unit (A1) derived from methyl methacrylate (hereinafter also referred to as "unit (A1)"), (meth)acrylic acid derived A repeating unit (A2) (hereinafter also referred to as “unit (A2)”), and a glutaric anhydride structural unit (A3) (hereinafter also referred to as “unit (A3)”) as a ring structural unit. coalescence is mentioned.
By including the unit (A3) in the polymer (A), it is easy to improve the heat resistance of the obtained resin molding. Unit (A3) is represented by the following chemical structural formula.
式中、ＲＡ及びＲＢは、それぞれ独立に、水素原子又はメチル基を示す。
In the formula, RA and RB each independently represent a hydrogen atom or a methyl group.
重合体（Ａ）中の単位（Ａ１）の含有割合の下限値は特に限定されない。得られた樹脂成形体が、透明性に優れ、加工性、機械的特性に優れるというアクリル樹脂本来の性能を損なわない観点から、重合体（Ａ）に含まれる繰り返し単位の総モル数（１００ｍｏｌ％）に対して、８０ｍｏｌ％が好ましく、９０ｍｏｌ％がより好ましく、９４ｍｏｌ％がさらに好ましい。重合体（Ａ）中の単位（Ａ１）の含有割合の上限値は特に限定されない。得られた樹脂成形体の耐熱性に優れる観点から、重合体（Ａ）に含まれる繰り返し単位の総モル数（１００ｍｏｌ％）に対して、９９．４ｍｏｌ％が好ましく、９９ｍｏｌ％がより好ましく、９８ｍｏｌ％がさらに好ましい。上記の上限値及び下限値は任意に組み合わせることができる。例えば、８０～９９．４ｍｏｌ％が好ましく、９０～９９ｍｏｌ％がより好ましく、９４～９８ｍｏｌ％がさらに好ましい。
The lower limit of the content of the units (A1) in the polymer (A) is not particularly limited. From the viewpoint that the obtained resin molding does not impair the original performance of the acrylic resin, which is excellent in transparency, workability, and mechanical properties, the total number of moles of repeating units contained in the polymer (A) (100 mol% ), preferably 80 mol %, more preferably 90 mol %, and even more preferably 94 mol %. The upper limit of the content of the units (A1) in the polymer (A) is not particularly limited. From the viewpoint of excellent heat resistance of the resulting resin molded product, it is preferably 99.4 mol%, more preferably 99 mol%, and 98 mol% with respect to the total number of moles (100 mol%) of the repeating units contained in the polymer (A). % is more preferred. The above upper limit and lower limit can be combined arbitrarily. For example, 80 to 99.4 mol% is preferred, 90 to 99 mol% is more preferred, and 94 to 98 mol% is even more preferred.
単位（Ａ２）としては、得られた樹脂成形体の耐熱性に優れることから、メタクリル酸が好ましい。
Methacrylic acid is preferable as the unit (A2) because the heat resistance of the obtained resin molding is excellent.
重合体（Ａ）中の単位（Ａ２）の含有割合の下限値は特に限定されない。得られた樹脂成形体の耐熱性、機械特性に優れる観点から、重合体（Ａ）に含まれる繰り返し単位の総モル数（１００ｍｏｌ％）に対して、０．５ｍｏｌ％が好ましく、１ｍｏｌ％がより好ましく、２ｍｏｌ％がさらに好ましい。重合体（Ａ）中の単位（Ａ２）の含有割合の上限値は特に限定されない。得られた樹脂成形体の成形外観、低吸水性、及び成形性に優れるというアクリル樹脂本来の性能を損なわない観点から、重合体（Ａ）に含まれる繰り返し単位の総モル数（１００ｍｏｌ％）に対して、２０ｍｏｌ％が好ましく、７ｍｏｌ％がより好ましく、３．５ｍｏｌ％がさらに好ましい。上記の上限値及び下限値は任意に組み合わせることができる。例えば、０．５～２０ｍｏｌ％が好ましく、１～７ｍｏｌ％がより好ましく、２～３．５ｍｏｌ％がさらに好ましい。
The lower limit of the content of the units (A2) in the polymer (A) is not particularly limited. From the viewpoint of excellent heat resistance and mechanical properties of the obtained resin molded product, it is preferably 0.5 mol%, more preferably 1 mol%, relative to the total number of moles (100 mol%) of the repeating units contained in the polymer (A). Preferably, 2 mol % is more preferable. The upper limit of the content of the units (A2) in the polymer (A) is not particularly limited. From the viewpoint of not impairing the original performance of the acrylic resin, such as excellent molding appearance, low water absorption, and moldability of the obtained resin molded product, the total number of moles (100 mol%) of the repeating units contained in the polymer (A) On the other hand, 20 mol % is preferred, 7 mol % is more preferred, and 3.5 mol % is even more preferred. The above upper limit and lower limit can be combined arbitrarily. For example, 0.5 to 20 mol% is preferred, 1 to 7 mol% is more preferred, and 2 to 3.5 mol% is even more preferred.
重合体（Ａ）中の単位（Ａ３）の含有割合の下限値は特に限定されない。得られた樹脂成形体が耐熱性に優れる観点から、重合体（Ａ）に含まれる繰り返し単位の総モル数（１００ｍｏｌ％）に対して、０．００１ｍｏｌ％が好ましく、０．０１ｍｏｌ％がより好ましく、０．０５ｍｏｌ％がさらに好ましい。重合体（Ａ）中の単位（Ａ３）の含有割合の上限値は、得られた樹脂成形体の成形着色の抑制、成形外観、及び耐候性に優れる観点から、１０ｍｏｌ％が好ましく、３ｍｏｌ％がより好ましく、０．３ｍｏｌ％がさらに好ましい。上記の上限値及び下限値は任意に組み合わせることができる。例えば、０．００１～１０ｍｏｌ％が好ましく、０．０１～３ｍｏｌ％がより好ましく、０．０５～０．３ｍｏｌ％がさらに好ましい。
The lower limit of the content of the units (A3) in the polymer (A) is not particularly limited. From the viewpoint that the obtained resin molding has excellent heat resistance, it is preferably 0.001 mol %, more preferably 0.01 mol %, relative to the total number of moles (100 mol %) of the repeating units contained in the polymer (A). , 0.05 mol % is more preferred. The upper limit of the content of the unit (A3) in the polymer (A) is preferably 10 mol%, and 3 mol%, from the viewpoints of suppressing molding coloration of the obtained resin molding, molding appearance, and excellent weather resistance. More preferably, 0.3 mol % is even more preferable. The above upper limit and lower limit can be combined arbitrarily. For example, 0.001 to 10 mol% is preferred, 0.01 to 3 mol% is more preferred, and 0.05 to 0.3 mol% is even more preferred.
単位（Ａ３）は、メタクリル酸メチル及び（メタ）アクリル酸を共重合させた共重合体において、単位（Ａ１）に由来するメトキシカルボニル基と、隣接する単位（Ａ２）に由来するカルボキシル基との環化反応により構築された単位であってもよい。
The unit (A3) is a copolymer obtained by copolymerizing methyl methacrylate and (meth)acrylic acid, and a methoxycarbonyl group derived from the unit (A1) and a carboxyl group derived from the adjacent unit (A2). It may be a unit constructed by a cyclization reaction.
本発明において、重合体中の各単位の含有率は、１Ｈ－ＮＭＲ測定から算出した値とする。具体的には、国際公開第２０１９／０１３１８６号に開示された方法を用いることができる。
In the present invention, the content of each unit in the polymer is a value calculated from 1 H-NMR measurement. Specifically, the method disclosed in WO2019/013186 can be used.
単位（Ａ１）、単位（Ａ２）及び単位（Ａ３）を含む重合体を製造する方法は特に限定されない。例えば、国際公開第２０１７／０２２３９３号、国際公開第２０１９／０１３１８６号に開示された製造方法を用いることができる。
The method for producing a polymer containing units (A1), units (A2) and units (A3) is not particularly limited. For example, the manufacturing methods disclosed in International Publication No. 2017/022393 and International Publication No. 2019/013186 can be used.
メタクリル系重合体の質量平均分子量は特に限定されない。好ましくは、５０，０００～１５０，０００とすることができ、７０，０００～１３０，０００が好ましい。メタクリル系重合体の質量平均分子量が前記下限値以上であると、得られた樹脂成形体の機械特性に優れる。メタクリル系重合体の質量平均分子量が前記上限値以下であると、熱板融着用メタクリル系樹脂組成物の流動性に優れる。
本発明において、質量平均分子量は、標準試料として標準ポリスチレンを用い、ゲルパーミエーションクロマトグラフィーを用いて測定した値とする。
メタクリル系重合体の質量平均分子量を制御するためには、単量体混合物の重合において連鎖移動剤の量を調整することが好ましい。 The mass average molecular weight of the methacrylic polymer is not particularly limited. Preferably, it can be between 50,000 and 150,000, preferably between 70,000 and 130,000. When the mass-average molecular weight of the methacrylic polymer is at least the lower limit, the mechanical properties of the obtained resin molding are excellent. When the mass average molecular weight of the methacrylic polymer is equal to or less than the upper limit, the fluidity of the methacrylic resin composition for hot plate welding is excellent.
In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography using standard polystyrene as a standard sample.
In order to control the weight average molecular weight of the methacrylic polymer, it is preferable to adjust the amount of the chain transfer agent in the polymerization of the monomer mixture.
本発明において、質量平均分子量は、標準試料として標準ポリスチレンを用い、ゲルパーミエーションクロマトグラフィーを用いて測定した値とする。
メタクリル系重合体の質量平均分子量を制御するためには、単量体混合物の重合において連鎖移動剤の量を調整することが好ましい。 The mass average molecular weight of the methacrylic polymer is not particularly limited. Preferably, it can be between 50,000 and 150,000, preferably between 70,000 and 130,000. When the mass-average molecular weight of the methacrylic polymer is at least the lower limit, the mechanical properties of the obtained resin molding are excellent. When the mass average molecular weight of the methacrylic polymer is equal to or less than the upper limit, the fluidity of the methacrylic resin composition for hot plate welding is excellent.
In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography using standard polystyrene as a standard sample.
In order to control the weight average molecular weight of the methacrylic polymer, it is preferable to adjust the amount of the chain transfer agent in the polymerization of the monomer mixture.
メタクリル系重合体の製造方法は特に限定されない。例えば、塊状重合法、懸濁重合法、乳化重合法、溶液重合法が挙げられる。生産性に優れる観点から、塊状重合法、懸濁重合法が好ましい。
The method for producing the methacrylic polymer is not particularly limited. Examples thereof include bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. A bulk polymerization method and a suspension polymerization method are preferable from the viewpoint of excellent productivity.
＜脂肪酸＞
本発明における脂肪酸は、熱板融着時に熱板から樹脂組成物を引き離す際に糸曳きを生じにくくし、また、射出成形時に金型からの離型性を良好なものとし、金型表面に樹脂組成物の剥離残渣を生じにくくするために添加する成分である。すなわち、本発明における脂肪酸は、樹脂組成物において、熱板融着時に熱板から樹脂組成物を引き離す際に糸曳きを生じにくくし、さらに、射出成形の金型からの離型性に優れたものとするための成分である。 <Fatty acid>
The fatty acid in the present invention makes it difficult for stringing to occur when the resin composition is separated from the hot plate during hot plate fusion, and also improves mold releasability during injection molding. It is a component that is added to make it difficult for the resin composition to leave a peeling residue. That is, the fatty acid in the present invention makes it difficult for the resin composition to string when the resin composition is separated from the hot plate during hot plate fusion, and furthermore, the resin composition has excellent releasability from the mold for injection molding. It is an ingredient for making things.
本発明における脂肪酸は、熱板融着時に熱板から樹脂組成物を引き離す際に糸曳きを生じにくくし、また、射出成形時に金型からの離型性を良好なものとし、金型表面に樹脂組成物の剥離残渣を生じにくくするために添加する成分である。すなわち、本発明における脂肪酸は、樹脂組成物において、熱板融着時に熱板から樹脂組成物を引き離す際に糸曳きを生じにくくし、さらに、射出成形の金型からの離型性に優れたものとするための成分である。 <Fatty acid>
The fatty acid in the present invention makes it difficult for stringing to occur when the resin composition is separated from the hot plate during hot plate fusion, and also improves mold releasability during injection molding. It is a component that is added to make it difficult for the resin composition to leave a peeling residue. That is, the fatty acid in the present invention makes it difficult for the resin composition to string when the resin composition is separated from the hot plate during hot plate fusion, and furthermore, the resin composition has excellent releasability from the mold for injection molding. It is an ingredient for making things.
脂肪酸としては、分子内にカルボキシル基を少なくとも１個有する鎖状炭化水素化合物が挙げられる。分子内にカルボキシル基を少なくとも１個有する鎖状炭化水素化合物とは、カルボキシル基が結合する炭素原子が炭素鎖の構成原子となっている化合物を意味する。分子内にカルボキシル基を少なくとも１個有する鎖状炭化水素化合物中の炭素鎖は、飽和であっても不飽和であってもよく、また、直鎖状であっても分枝鎖状であってもよい。
脂肪酸としては、カルボキシル基を１個有する鎖状炭化水素化合物が好ましい。カルボキシル基が１個であると、溶融混練や溶融成形の際に、メタクリル系重合体の反応性官能基との架橋反応による高分子量化が起こらず、流動性が低下しにくい。 Fatty acids include chain hydrocarbon compounds having at least one carboxyl group in the molecule. A chain hydrocarbon compound having at least one carboxyl group in the molecule means a compound in which the carbon atom to which the carboxyl group is bonded is a constituent atom of the carbon chain. The carbon chain in the chain hydrocarbon compound having at least one carboxyl group in the molecule may be saturated or unsaturated, and may be linear or branched. good too.
A chain hydrocarbon compound having one carboxyl group is preferable as the fatty acid. When the number of carboxyl groups is one, during melt-kneading or melt-molding, high molecular weight formation due to a cross-linking reaction with the reactive functional group of the methacrylic polymer does not occur, and fluidity is less likely to decrease.
脂肪酸としては、カルボキシル基を１個有する鎖状炭化水素化合物が好ましい。カルボキシル基が１個であると、溶融混練や溶融成形の際に、メタクリル系重合体の反応性官能基との架橋反応による高分子量化が起こらず、流動性が低下しにくい。 Fatty acids include chain hydrocarbon compounds having at least one carboxyl group in the molecule. A chain hydrocarbon compound having at least one carboxyl group in the molecule means a compound in which the carbon atom to which the carboxyl group is bonded is a constituent atom of the carbon chain. The carbon chain in the chain hydrocarbon compound having at least one carboxyl group in the molecule may be saturated or unsaturated, and may be linear or branched. good too.
A chain hydrocarbon compound having one carboxyl group is preferable as the fatty acid. When the number of carboxyl groups is one, during melt-kneading or melt-molding, high molecular weight formation due to a cross-linking reaction with the reactive functional group of the methacrylic polymer does not occur, and fluidity is less likely to decrease.
脂肪酸の１０％重量減少温度の上限は特に限定されない。射出成形時の金型からの離型性や、得られた樹脂成形体の熱板融着性がより良好となる観点から、２５０℃以下が好ましく、２４０℃以下がより好ましく、２３０℃以下がさらに好ましい。１０％重量減少温度が前記上限値以下であると、熱板融着時に、樹脂成形体に含まれる脂肪酸が溶融部に局在化して糸曳きが生じにくくなり、また、射出成形時に、メタクリル系樹脂組成物に含まれる脂肪酸が金型内で揮発しやすくなり、その結果、後から金型内に注入されたメタクリル系樹脂組成物に、金型表面に付着して液化又は凝縮した脂肪酸が拡散、移行することで、最終的に得られた樹脂成形体の表面及び表面の近傍に、脂肪酸が高い含有割合で存在するためと推察している。
The upper limit of the 10% weight loss temperature of fatty acids is not particularly limited. It is preferably 250° C. or lower, more preferably 240° C. or lower, more preferably 230° C. or lower, from the viewpoint of better releasability from the mold during injection molding and better hot plate fusion of the obtained resin molded product. More preferred. When the 10% weight loss temperature is equal to or lower than the above upper limit, the fatty acid contained in the resin molded body is localized in the melted portion during hot plate fusion, making it difficult for stringing to occur. The fatty acid contained in the resin composition is easily volatilized in the mold, and as a result, the liquefied or condensed fatty acid adhering to the mold surface diffuses into the methacrylic resin composition injected into the mold later. , and migrating, the fatty acid is present at a high content on the surface and in the vicinity of the surface of the finally obtained resin molding.
脂肪酸の１０％重量減少温度の下限は特に限定されない。射出成形時の金型からの離型性や、得られた樹脂成形体の熱板融着性がより良好となる観点から、１５０℃以上が好ましく、１７０℃以上がより好ましく、２００℃以上がさらに好ましい。１０％重量減少温度が前記下限値以上であると、熱板融着時に、脂肪酸が樹脂成形体から過剰に揮発して、熱板離型性が低下してしまうことが抑制され、また、射出成形時には、金型内で揮発した脂肪酸が金型表面に付着して液化又は凝縮しやすくなり、その結果、金型のガスベントからガスとして排出される脂肪酸の量が少なくなることが抑制され、得られた樹脂成形体の表面及び表面の近傍に脂肪酸が高い含有割合で存在できるためと推察している。
The lower limit of the 10% weight loss temperature of fatty acids is not particularly limited. It is preferably 150° C. or higher, more preferably 170° C. or higher, and 200° C. or higher from the viewpoint of better releasability from the mold during injection molding and better hot plate fusion of the obtained resin molded product. More preferred. If the 10% weight loss temperature is equal to or higher than the above lower limit, excessive volatilization of fatty acids from the resin molded article during hot plate fusion is suppressed, and deterioration of hot plate releasability is suppressed. During molding, the fatty acid volatilized in the mold adheres to the mold surface and tends to liquefy or condense. As a result, the amount of fatty acid discharged as gas from the gas vent of the mold is suppressed, It is presumed that this is because a high content of fatty acids can be present on the surface and in the vicinity of the surface of the molded resin article.
脂肪酸の１０％重量減少温度の上記の上限値及び下限値は任意に組み合わせることができる。例えば、脂肪酸の１０％重量減少温度は１５０～２５０℃が好ましく、１７０～２４０℃がより好ましく、２００～２３０℃がさらに好ましい。
The above upper limit and lower limit of the 10% weight loss temperature of fatty acids can be combined arbitrarily. For example, the 10% weight loss temperature of fatty acids is preferably 150 to 250°C, more preferably 170 to 240°C, even more preferably 200 to 230°C.
脂肪酸の融点の下限は特に限定されない。射出成形時の金型からの離型性がより良好となり、さらに、得られた樹脂成形体の熱板融着性がより良好となる観点から、５０℃以上が好ましく、５５℃以上がより好ましく６０℃以上がさらに好ましい。脂肪酸の融点が前記下限値以上であると、熱板融着時にメタクリル系樹脂組成物の粘度低下を抑制できるので、糸曳きが生じにくくなり、また、メタクリル系樹脂組成物に含まれる脂肪酸が、射出成形時に樹脂が金型に充填される際、溶融樹脂内で拡散しやすくなり、その結果、後から金型内に注入されたメタクリル系樹脂組成物に、金型表面に付着して液化又は凝縮した脂肪酸が拡散、移行することで、最終的に得られた樹脂成形体の表面及び表面の近傍に、脂肪酸が高い含有割合で存在するためと推察している。
The lower limit of the melting point of fatty acids is not particularly limited. The temperature is preferably 50° C. or higher, more preferably 55° C. or higher, from the viewpoint of better releasability from the mold during injection molding and better hot-plate fusion bonding of the resulting resin molded product. 60° C. or higher is more preferable. When the melting point of the fatty acid is at least the above lower limit, the decrease in the viscosity of the methacrylic resin composition during hot plate fusion can be suppressed, so stringing is less likely to occur, and the fatty acid contained in the methacrylic resin composition When the resin is filled into the mold during injection molding, it becomes easier to diffuse in the molten resin. It is speculated that the condensed fatty acid diffuses and migrates, resulting in a high fatty acid content on the surface and in the vicinity of the surface of the finally obtained resin molding.
脂肪酸の融点の上限は特に限定されない。得られた樹脂成形体の熱板融着性がより良好となる観点から、１００℃以下が好ましく、９０℃以下がより好ましく、８０℃以下がさらに好ましい。脂肪酸の融点が前記上限値以下であると、熱板融着時に樹脂成形体中の脂肪酸が有する糸曳き抑制の効果が得られやすくなり、また、射出成形時に金型内で揮発した脂肪酸が、金型表面で液化又は凝縮して、脂肪酸からなる被膜層が金型表面に形成されやすくなり、その結果、上述した作用、効果を得やすくなるためと推察している。
The upper limit of the melting point of fatty acids is not particularly limited. From the viewpoint of better hot-plate fusion bondability of the obtained resin molding, the temperature is preferably 100° C. or lower, more preferably 90° C. or lower, and even more preferably 80° C. or lower. When the melting point of the fatty acid is equal to or lower than the above upper limit, the effect of suppressing the stringing of the fatty acid in the resin molded product during hot plate fusion is easily obtained, and the fatty acid volatilized in the mold during injection molding is It is presumed that the fatty acid is liquefied or condensed on the mold surface to facilitate the formation of a film layer composed of fatty acids on the mold surface, and as a result, the above-described functions and effects can be easily obtained.
脂肪酸の融点の上記の上限値及び下限値は任意に組み合わせることができる。例えば、脂肪酸の融点は、５０～１００℃が好ましく、５５～９０℃がより好ましく、６０～８０℃がさらに好ましい。
The above upper limit and lower limit of the melting point of fatty acids can be combined arbitrarily. For example, the melting point of the fatty acid is preferably 50-100°C, more preferably 55-90°C, even more preferably 60-80°C.
脂肪酸の分子量は特に限定されない。分子量が１００～５００の脂肪酸を用いることができ、２００～４００がより好ましい。脂肪酸の分子量が前記下限値以上であれば、脂肪酸の揮発性が低いため、射出成形するときの金型からの離型性や、熱板融着性の向上に対して十分な効果が得られる。脂肪酸の分子量が前記上限値以下であれば、メタクリル系重合体との相溶性が高いため、射出成形するときの金型からの離型性や熱板融着するときの熱板からの糸曳きが抑制され、また、熱板や金型から離す際に熱板や金型表面への脂肪酸の残存が少なくなるため、熱板や金型の表面汚れ、得られた樹脂成形体の曇りが発生しにくい。
The molecular weight of fatty acids is not particularly limited. Fatty acids with a molecular weight of 100-500 can be used, with 200-400 being more preferred. When the molecular weight of the fatty acid is at least the above lower limit, the volatility of the fatty acid is low, and sufficient effects can be obtained for improving releasability from the mold during injection molding and hot plate fusion bonding. . If the molecular weight of the fatty acid is equal to or less than the above upper limit, the compatibility with the methacrylic polymer is high, so that it is easy to release from the mold during injection molding and stringing from the hot plate during hot plate fusion. Also, when the hot plate and mold are separated from the hot plate and the mold, less fatty acid remains on the surface of the hot plate and mold, so the surface of the hot plate and mold becomes dirty, and the obtained resin molding becomes cloudy. hard to do.
脂肪酸の炭素数は特に限定されない。好ましくは、１０～２２である。炭素数が前記下限値以上であれば、脂肪酸の揮発性が低いため、射出成形するときの金型からの離型性や、熱板融着時に熱板から引き離す際に、糸曳きが生じにくくなりやすい。炭素数が前記上限値以下であれば、メタクリル系重合体との相溶性が高いため、金型からの離型性と熱板融着性に優れ、また、熱板や金型から引き離す際に熱板や金型表面への脂肪酸の残存が少なくなるため、熱板や金型の表面汚れや、得られた樹脂成形体の曇りが発生しにくい。
The number of carbon atoms in fatty acids is not particularly limited. Preferably, it is 10-22. If the number of carbon atoms is at least the above lower limit, the volatility of the fatty acid is low, so that stringiness is less likely to occur when releasing from the mold during injection molding and when separating from the hot plate during hot plate fusion bonding. Prone. If the number of carbon atoms is equal to or less than the above upper limit, the compatibility with the methacrylic polymer is high, so the releasability from the mold and hot plate fusion are excellent, and when separating from the hot plate and the mold, Since the amount of fatty acid remaining on the surface of the hot plate and mold is reduced, the surface of the hot plate and mold is less likely to be stained, and the obtained resin molding is less likely to be cloudy.
脂肪酸としては、例えば、ラウリル酸、パルミチン酸、ステアリン酸、ミリスチン酸、ベヘン酸のような飽和脂肪酸や、オレイン酸、リノール酸のような不飽和脂肪酸が挙げられ、ステアリン酸、パルミチン酸、ミリスチン酸が好ましい。
脂肪酸は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of fatty acids include saturated fatty acids such as lauric acid, palmitic acid, stearic acid, myristic acid and behenic acid, and unsaturated fatty acids such as oleic acid and linoleic acid. is preferred.
A fatty acid may be used individually by 1 type, and may use 2 or more types together.
脂肪酸は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of fatty acids include saturated fatty acids such as lauric acid, palmitic acid, stearic acid, myristic acid and behenic acid, and unsaturated fatty acids such as oleic acid and linoleic acid. is preferred.
A fatty acid may be used individually by 1 type, and may use 2 or more types together.
本発明のメタクリル系樹脂組成物中の脂肪酸の含有量は特に限定されない。メタクリル系重合体１００質量部に対して、０．０１～１質量部とすることができ、０．１～０．３質量部がより好ましい。脂肪酸の含有割合が前記下限値以上であれば、射出成形するときの金型からの離型性や、熱板融着性が向上しやすい。前記上限値以下であれば、熱板や金型から引き離す際に熱板や金型表面への脂肪酸の残存が少なくなるため、熱板や金型の表面汚れや、得られた樹脂成形体の曇りが発生しにくい。
The content of fatty acid in the methacrylic resin composition of the present invention is not particularly limited. It can be 0.01 to 1 part by mass, more preferably 0.1 to 0.3 part by mass, with respect to 100 parts by mass of the methacrylic polymer. When the fatty acid content is at least the above lower limit, releasability from molds during injection molding and hot-plate fusion bonding are likely to be improved. If it is less than the above upper limit, the amount of fatty acid remaining on the surface of the hot plate and the mold is reduced when the hot plate and the mold are separated, so the surface of the hot plate and the mold is dirty, and the obtained resin molded body is reduced. Cloudiness is less likely to occur.
本発明のメタクリル系樹脂組成物中の脂肪酸の含有割合は特に限定されない。本発明のメタクリル系樹脂組成物の総質量（１００質量％）に対して、０．０１～１質量％とすることができ、０．１～０．３質量％がより好ましい。脂肪酸の含有割合が前記下限値以上であれば、射出成形するときの金型からの離型性や、熱板融着性が向上しやすい。前記上限値以下であれば、熱板や金型から引き離す際に熱板や金型表面への脂肪酸の残存が少なくなるため、熱板や金型の表面汚れや、得られた樹脂成形体の曇りが発生しにくい。
The content of fatty acids in the methacrylic resin composition of the present invention is not particularly limited. It can be 0.01 to 1% by mass, more preferably 0.1 to 0.3% by mass, relative to the total mass (100% by mass) of the methacrylic resin composition of the present invention. When the fatty acid content is at least the above lower limit, the releasability from the mold during injection molding and the hot plate fusion bondability are likely to be improved. If it is less than the upper limit, the amount of fatty acid remaining on the surface of the hot plate and the mold is reduced when the hot plate and the mold are separated. Cloudiness is less likely to occur.
＜他の添加剤＞
本発明のメタクリル系樹脂組成物には、本発明の効果に影響を及ぼさない範囲内で、必要に応じて、他の添加剤、例えば、紫外線吸収剤、光拡散剤、酸化防止剤、着色剤、顔料、染料、熱安定化剤、補強剤、充填材、難燃剤、発泡剤、滑剤、可塑剤、帯電防止剤を含有させてもよい。 <Other additives>
If necessary, the methacrylic resin composition of the present invention may contain other additives such as ultraviolet absorbers, light diffusing agents, antioxidants, and colorants within a range that does not affect the effects of the present invention. , pigments, dyes, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants, plasticizers and antistatic agents.
本発明のメタクリル系樹脂組成物には、本発明の効果に影響を及ぼさない範囲内で、必要に応じて、他の添加剤、例えば、紫外線吸収剤、光拡散剤、酸化防止剤、着色剤、顔料、染料、熱安定化剤、補強剤、充填材、難燃剤、発泡剤、滑剤、可塑剤、帯電防止剤を含有させてもよい。 <Other additives>
If necessary, the methacrylic resin composition of the present invention may contain other additives such as ultraviolet absorbers, light diffusing agents, antioxidants, and colorants within a range that does not affect the effects of the present invention. , pigments, dyes, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants, plasticizers and antistatic agents.
＜熱板融着用メタクリル系樹脂組成物の製造方法＞
本発明のメタクリル系樹脂組成物の製造方法としては、例えば、下記（１）及び（２）の方法が挙げられる。
（１）メタクリル系重合体と脂肪酸とを、単独押出機や二軸押出機に投入し、加熱溶融して混練することにより混合する方法。
（２）メタクリル酸メチルを主成分とする単量体に脂肪酸を混合して重合する方法。 <Method for producing methacrylic resin composition for hot plate welding>
Examples of the method for producing the methacrylic resin composition of the present invention include the following methods (1) and (2).
(1) A method in which a methacrylic polymer and a fatty acid are charged into a single extruder or a twin-screw extruder, heated, melted, and kneaded to mix.
(2) A method in which a monomer containing methyl methacrylate as a main component is mixed with a fatty acid and polymerized.
本発明のメタクリル系樹脂組成物の製造方法としては、例えば、下記（１）及び（２）の方法が挙げられる。
（１）メタクリル系重合体と脂肪酸とを、単独押出機や二軸押出機に投入し、加熱溶融して混練することにより混合する方法。
（２）メタクリル酸メチルを主成分とする単量体に脂肪酸を混合して重合する方法。 <Method for producing methacrylic resin composition for hot plate welding>
Examples of the method for producing the methacrylic resin composition of the present invention include the following methods (1) and (2).
(1) A method in which a methacrylic polymer and a fatty acid are charged into a single extruder or a twin-screw extruder, heated, melted, and kneaded to mix.
(2) A method in which a monomer containing methyl methacrylate as a main component is mixed with a fatty acid and polymerized.
本発明のメタクリル系樹脂組成物は、熱板融着時に熱板から樹脂組成物を引き離す際に糸曳きを生じにくく、また、射出成形時に金型表面に樹脂組成物の剥離残渣が生じにくい。そのため、本発明のメタクリル系樹脂組成物を射出成形して得られた樹脂成形体は、熱板融着用の部材として好適に使用できる。
The methacrylic resin composition of the present invention is less likely to cause stringing when the resin composition is separated from the hot plate during hot plate fusion, and less likely to leave a peeling residue of the resin composition on the mold surface during injection molding. Therefore, a resin molded article obtained by injection molding the methacrylic resin composition of the present invention can be suitably used as a member for hot plate welding.
＜融着方法＞
本発明の融着方法は、本発明のメタクリル系樹脂組成物から形成された第１の部材の少なくとも一部を熱板に接触させて溶融させる工程と、第１の部材を熱板から引き離し、第２の部材と圧着する工程とを備える。
第２の部材の材質としては、本発明のメタクリル系重合体と熱融着する材質であれば特に限定されない。例えば、ＡＢＳ、ＳＡＮ、ＡＳ、ＭＳ樹脂等のスチレン系樹脂や、ポリカーボネート系樹脂、ポリ塩化ビニル系樹脂が挙げられる。第２の部材として、本発明のメタクリル系樹脂組成物から形成された部材を用いることもできる。 <fusion method>
The fusion bonding method of the present invention includes the steps of bringing at least part of a first member formed from the methacrylic resin composition of the present invention into contact with a hot plate to melt it, separating the first member from the hot plate, crimping with the second member.
The material of the second member is not particularly limited as long as it is heat-sealable with the methacrylic polymer of the present invention. Examples include styrene-based resins such as ABS, SAN, AS, and MS resins, polycarbonate-based resins, and polyvinyl chloride-based resins. A member formed from the methacrylic resin composition of the present invention can also be used as the second member.
本発明の融着方法は、本発明のメタクリル系樹脂組成物から形成された第１の部材の少なくとも一部を熱板に接触させて溶融させる工程と、第１の部材を熱板から引き離し、第２の部材と圧着する工程とを備える。
第２の部材の材質としては、本発明のメタクリル系重合体と熱融着する材質であれば特に限定されない。例えば、ＡＢＳ、ＳＡＮ、ＡＳ、ＭＳ樹脂等のスチレン系樹脂や、ポリカーボネート系樹脂、ポリ塩化ビニル系樹脂が挙げられる。第２の部材として、本発明のメタクリル系樹脂組成物から形成された部材を用いることもできる。 <fusion method>
The fusion bonding method of the present invention includes the steps of bringing at least part of a first member formed from the methacrylic resin composition of the present invention into contact with a hot plate to melt it, separating the first member from the hot plate, crimping with the second member.
The material of the second member is not particularly limited as long as it is heat-sealable with the methacrylic polymer of the present invention. Examples include styrene-based resins such as ABS, SAN, AS, and MS resins, polycarbonate-based resins, and polyvinyl chloride-based resins. A member formed from the methacrylic resin composition of the present invention can also be used as the second member.
図１は、本発明の融着方法の一態様を示す工程図である。
第１の部材１と第２の部材２との間に熱板３を配置し（図１（ａ））、第１の部材１及び第２の部材２の少なくとも一部を熱板３に接触させてそれぞれ溶融させた後（図１（ｂ））、熱板４から引き離して（図１（ｃ））、第１の部材の溶融部１ａと第２の部材の溶融部２ａとを融着（圧着）して、第１の部材１と第２の部材２を接合することができる（図１（ｄ））。 FIG. 1 is a process diagram showing one embodiment of the fusion bonding method of the present invention.
Ahot plate 3 is placed between the first member 1 and the second member 2 (FIG. 1(a)), and at least a part of the first member 1 and the second member 2 is brought into contact with the hot plate 3. 1(b)), separated from the hot plate 4 (FIG. 1(c)), and melted portion 1a of the first member and melted portion 2a of the second member are fused together. (Crimping), the first member 1 and the second member 2 can be joined (FIG. 1(d)).
第１の部材１と第２の部材２との間に熱板３を配置し（図１（ａ））、第１の部材１及び第２の部材２の少なくとも一部を熱板３に接触させてそれぞれ溶融させた後（図１（ｂ））、熱板４から引き離して（図１（ｃ））、第１の部材の溶融部１ａと第２の部材の溶融部２ａとを融着（圧着）して、第１の部材１と第２の部材２を接合することができる（図１（ｄ））。 FIG. 1 is a process diagram showing one embodiment of the fusion bonding method of the present invention.
A
＜車両用部材＞
本発明の車両用部材は、第１の部材と第２の部材とを接着してなる複合部材を含む。
本発明の車両用部材における第１の部材は、メタクリル系重合体および脂肪酸を含む。本発明の車両用部材における第１の部材は、本発明のメタクリル系樹脂組成物から形成された部材であってよい。
第１の部材と第２の部材とを接着してなる複合部材は、第１の部材と第２の部材とが融着されて形成されていてもよい。 <Vehicle parts>
A vehicle member of the present invention includes a composite member formed by bonding a first member and a second member.
The first member in the vehicle member of the present invention contains a methacrylic polymer and a fatty acid. The first member in the vehicle member of the present invention may be a member formed from the methacrylic resin composition of the present invention.
A composite member formed by bonding the first member and the second member may be formed by fusing the first member and the second member.
本発明の車両用部材は、第１の部材と第２の部材とを接着してなる複合部材を含む。
本発明の車両用部材における第１の部材は、メタクリル系重合体および脂肪酸を含む。本発明の車両用部材における第１の部材は、本発明のメタクリル系樹脂組成物から形成された部材であってよい。
第１の部材と第２の部材とを接着してなる複合部材は、第１の部材と第２の部材とが融着されて形成されていてもよい。 <Vehicle parts>
A vehicle member of the present invention includes a composite member formed by bonding a first member and a second member.
The first member in the vehicle member of the present invention contains a methacrylic polymer and a fatty acid. The first member in the vehicle member of the present invention may be a member formed from the methacrylic resin composition of the present invention.
A composite member formed by bonding the first member and the second member may be formed by fusing the first member and the second member.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されない。
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
〔射出成形時の離型性〕
射出成形時の離型性の指標として、下記の方法で突き出しピン圧力を測定した。
実施例及び比較例で得られたペレット状のメタクリル系樹脂組成物を、８０℃で約１６時間熱風乾燥した後に、シリンダー温度２６０℃に設定した射出成形機（機種名：ＥＣ７５－ＳＸＩＩ、芝浦機械製（株）製）に供給し、ガス抜け部を設けた金型（縦直径７５ｍｍ、厚さ３ｍｍの円盤状の成形品（４）（図２）を成形できる。この円盤状の金型の中心にゲート部を有する。成形品を離型するための突き出しピンが、円盤状の金型の中央部に１本、金型の周縁部に等間隔で４本配置されている。）を用いて金型温度９０℃、射出圧力８０ＭＰａの条件で連続成形を行い、中央部の突出しピンの裏に設置した圧力センサにより、成形品（４）を金型から離型する時の突き出しピン圧力（単位：ＭＰａ）を測定した。突き出しピン圧力の値が低いほど、離型性が優れている。 [Releasability during injection molding]
As an index of releasability during injection molding, the ejector pin pressure was measured by the following method.
The pellet-shaped methacrylic resin compositions obtained in Examples and Comparative Examples were dried with hot air at 80 ° C. for about 16 hours, and then an injection molding machine (model name: EC75-SXII, Shibaura Kikai) set at a cylinder temperature of 260 ° C. (manufactured by Co., Ltd.), and a mold provided with a gas vent (75 mm in vertical diameter and 3 mm in thickness) (4) (Fig. 2) can be molded. It has a gate part in the center.Ejection pins for releasing the molded product are arranged one in the center part of the disk-shaped mold and four in the peripheral part of the mold at equal intervals. Continuous molding is performed under the conditions of a mold temperature of 90 ° C and an injection pressure of 80 MPa, and a pressure sensor installed on the back of the central ejector pin detects the ejector pin pressure ( Unit: MPa) was measured. The lower the ejector pin pressure value, the better the releasability.
射出成形時の離型性の指標として、下記の方法で突き出しピン圧力を測定した。
実施例及び比較例で得られたペレット状のメタクリル系樹脂組成物を、８０℃で約１６時間熱風乾燥した後に、シリンダー温度２６０℃に設定した射出成形機（機種名：ＥＣ７５－ＳＸＩＩ、芝浦機械製（株）製）に供給し、ガス抜け部を設けた金型（縦直径７５ｍｍ、厚さ３ｍｍの円盤状の成形品（４）（図２）を成形できる。この円盤状の金型の中心にゲート部を有する。成形品を離型するための突き出しピンが、円盤状の金型の中央部に１本、金型の周縁部に等間隔で４本配置されている。）を用いて金型温度９０℃、射出圧力８０ＭＰａの条件で連続成形を行い、中央部の突出しピンの裏に設置した圧力センサにより、成形品（４）を金型から離型する時の突き出しピン圧力（単位：ＭＰａ）を測定した。突き出しピン圧力の値が低いほど、離型性が優れている。 [Releasability during injection molding]
As an index of releasability during injection molding, the ejector pin pressure was measured by the following method.
The pellet-shaped methacrylic resin compositions obtained in Examples and Comparative Examples were dried with hot air at 80 ° C. for about 16 hours, and then an injection molding machine (model name: EC75-SXII, Shibaura Kikai) set at a cylinder temperature of 260 ° C. (manufactured by Co., Ltd.), and a mold provided with a gas vent (75 mm in vertical diameter and 3 mm in thickness) (4) (Fig. 2) can be molded. It has a gate part in the center.Ejection pins for releasing the molded product are arranged one in the center part of the disk-shaped mold and four in the peripheral part of the mold at equal intervals. Continuous molding is performed under the conditions of a mold temperature of 90 ° C and an injection pressure of 80 MPa, and a pressure sensor installed on the back of the central ejector pin detects the ejector pin pressure ( Unit: MPa) was measured. The lower the ejector pin pressure value, the better the releasability.
〔射出成形後の成形外観〕
射出成形後の成形外観の指標として、下記の方法で剥離不良の有無を観察した。
離型性の評価と同様の方法で、円盤状の成形品（４）を４０ショット連続成形した。得られた成形品（４）の表面を目視で観察し、成形品（４）の表面に金型からの剥離不良による表面荒れが１ショットでも観察された場合、剥離不良と判定した。 [Molding appearance after injection molding]
As an index of molded appearance after injection molding, the presence or absence of poor peeling was observed by the following method.
A disc-shaped molded product (4) was continuously molded for 40 shots in the same manner as the evaluation of releasability. The surface of the obtained molded product (4) was visually observed, and when even one shot of surface roughness due to poor peeling from the mold was observed on the surface of the molded product (4), it was determined to be defective in peeling.
射出成形後の成形外観の指標として、下記の方法で剥離不良の有無を観察した。
離型性の評価と同様の方法で、円盤状の成形品（４）を４０ショット連続成形した。得られた成形品（４）の表面を目視で観察し、成形品（４）の表面に金型からの剥離不良による表面荒れが１ショットでも観察された場合、剥離不良と判定した。 [Molding appearance after injection molding]
As an index of molded appearance after injection molding, the presence or absence of poor peeling was observed by the following method.
A disc-shaped molded product (4) was continuously molded for 40 shots in the same manner as the evaluation of releasability. The surface of the obtained molded product (4) was visually observed, and when even one shot of surface roughness due to poor peeling from the mold was observed on the surface of the molded product (4), it was determined to be defective in peeling.
〔熱板融着性〕
熱板融着性の指標として、下記の方法で糸曳き性を観察した。
・試験片作製：離型性の評価で成形した円盤状の成形品（４）（縦直径７５ｍｍ、厚さ３ｍｍ）からスプルー部（５）を切断して、円錐状の試験片（６）（底面の直径１０ｍｍ、高さ７０ｍｍ）を作製した（図２及び図３を参照）。
・熱板：ホットプレート（７）上にＳＵＳ３０４製のプレートを敷き、これを熱板（８）とした。プローブ型温度計で熱板（８）の表面温度を実測することにより、熱板表面の温度管理を行なった。
・試験方法：熱板（８）の表面温度が２６０℃となるように加熱した後、円錐状の試験片（６）の底面部（９）（直径１０ｍｍ）を熱板（８）の表面に２０秒間接触させ、接触部を溶融させた後、高さ３０ｃｍまで試験片（６）を引き上げ、試験片（６）と熱板（８）との間の糸曳きの発生の有無を確認した（図４参照）。糸曳きとは、糸状のメタクリル系樹脂組成物の一部である。試験片５点を用意し、各試験片について１回ずつ上記の操作を行い、以下の判定基準に従って判定した。
（判定基準）
Ａ：糸曳き有りが０回
Ｂ：糸曳き有りが１～２回
Ｃ：糸曳き有りが３～５回 [Hot plate adhesion]
As an index of hot plate fusion bondability, stringiness was observed by the following method.
- Test piece preparation: The sprue portion (5) was cut from the disk-shaped molded product (4) (vertical diameter 75 mm,thickness 3 mm) molded for mold release evaluation, and a conical test piece (6) ( 10 mm in bottom diameter and 70 mm in height) were fabricated (see FIGS. 2 and 3).
Hot plate: A plate made of SUS304 was placed on the hot plate (7), and this was used as the hot plate (8). The temperature of the hot plate surface was controlled by actually measuring the surface temperature of the hot plate (8) with a probe thermometer.
・Test method: After heating the surface temperature of the hot plate (8) to 260 ° C., the bottom part (9) (diameter 10 mm) of the conical test piece (6) is placed on the surface of the hot plate (8). After contacting for 20 seconds and melting the contact portion, the test piece (6) was pulled up to a height of 30 cm, and the presence or absence of stringing between the test piece (6) and the hot plate (8) was confirmed ( See Figure 4). Stringing is part of the thread-like methacrylic resin composition. Five test pieces were prepared, the above operation was performed once for each test piece, and evaluation was made according to the following criteria.
(criterion)
A: Stringing 0 times B: Stringing 1-2 times C: Stringing 3-5 times
熱板融着性の指標として、下記の方法で糸曳き性を観察した。
・試験片作製：離型性の評価で成形した円盤状の成形品（４）（縦直径７５ｍｍ、厚さ３ｍｍ）からスプルー部（５）を切断して、円錐状の試験片（６）（底面の直径１０ｍｍ、高さ７０ｍｍ）を作製した（図２及び図３を参照）。
・熱板：ホットプレート（７）上にＳＵＳ３０４製のプレートを敷き、これを熱板（８）とした。プローブ型温度計で熱板（８）の表面温度を実測することにより、熱板表面の温度管理を行なった。
・試験方法：熱板（８）の表面温度が２６０℃となるように加熱した後、円錐状の試験片（６）の底面部（９）（直径１０ｍｍ）を熱板（８）の表面に２０秒間接触させ、接触部を溶融させた後、高さ３０ｃｍまで試験片（６）を引き上げ、試験片（６）と熱板（８）との間の糸曳きの発生の有無を確認した（図４参照）。糸曳きとは、糸状のメタクリル系樹脂組成物の一部である。試験片５点を用意し、各試験片について１回ずつ上記の操作を行い、以下の判定基準に従って判定した。
（判定基準）
Ａ：糸曳き有りが０回
Ｂ：糸曳き有りが１～２回
Ｃ：糸曳き有りが３～５回 [Hot plate adhesion]
As an index of hot plate fusion bondability, stringiness was observed by the following method.
- Test piece preparation: The sprue portion (5) was cut from the disk-shaped molded product (4) (vertical diameter 75 mm,
Hot plate: A plate made of SUS304 was placed on the hot plate (7), and this was used as the hot plate (8). The temperature of the hot plate surface was controlled by actually measuring the surface temperature of the hot plate (8) with a probe thermometer.
・Test method: After heating the surface temperature of the hot plate (8) to 260 ° C., the bottom part (9) (
(criterion)
A: Stringing 0 times B: Stringing 1-2 times C: Stringing 3-5 times
＜融点＞
脂肪酸の融点を、示差走査熱量計（ＤＳＣ）（セイコーインスツル社製、型式：ＤＳＣ－６２００）を用いて、下記の方法で評価した。
脂肪酸約１０ｍｇを、アルミニウム製のサンプル容器に入れ、昇温速度１０℃／分で２００℃まで昇温して５分間保持して溶融させた後、１０℃／分で０℃まで降温して、再度昇温速度１０℃／分で昇温、５分間保持、１０℃／分で降温を行い、この時に観察された結晶融解ピークの最大点を、脂肪酸の融点とした。 <Melting point>
The melting points of fatty acids were evaluated by the following method using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., model: DSC-6200).
About 10 mg of fatty acid is placed in an aluminum sample container, heated to 200° C. at a temperature increase rate of 10° C./min, held for 5 minutes to melt, and then cooled to 0° C. at 10° C./min. The temperature was again raised at a temperature elevation rate of 10°C/min, held for 5 minutes, and then lowered at 10°C/min.
脂肪酸の融点を、示差走査熱量計（ＤＳＣ）（セイコーインスツル社製、型式：ＤＳＣ－６２００）を用いて、下記の方法で評価した。
脂肪酸約１０ｍｇを、アルミニウム製のサンプル容器に入れ、昇温速度１０℃／分で２００℃まで昇温して５分間保持して溶融させた後、１０℃／分で０℃まで降温して、再度昇温速度１０℃／分で昇温、５分間保持、１０℃／分で降温を行い、この時に観察された結晶融解ピークの最大点を、脂肪酸の融点とした。 <Melting point>
The melting points of fatty acids were evaluated by the following method using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., model: DSC-6200).
About 10 mg of fatty acid is placed in an aluminum sample container, heated to 200° C. at a temperature increase rate of 10° C./min, held for 5 minutes to melt, and then cooled to 0° C. at 10° C./min. The temperature was again raised at a temperature elevation rate of 10°C/min, held for 5 minutes, and then lowered at 10°C/min.
＜１０％重量減少温度＞
脂肪酸の１０％重量減少温度を、熱重量測定装置（ＴＧＡ）（セイコーインスツルメンツ株式会社製、型式：ＴＧ／ＤＴＡ６２００）を用いて、下記の方法に従って測定した。乾燥窒素を１００ｍｌ／分で流しながら、昇温速度１０℃／分で４０℃から５００℃まで昇温し、重量減少率１０％（重量が１０質量％減少すること）となる温度を測定した。 <10% Weight Loss Temperature>
The 10% weight loss temperature of fatty acids 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 raised from 40° C. to 500° C. at a heating rate of 10° C./min, and the temperature at which the weight reduction rate was 10% (10% by mass reduction) was measured.
脂肪酸の１０％重量減少温度を、熱重量測定装置（ＴＧＡ）（セイコーインスツルメンツ株式会社製、型式：ＴＧ／ＤＴＡ６２００）を用いて、下記の方法に従って測定した。乾燥窒素を１００ｍｌ／分で流しながら、昇温速度１０℃／分で４０℃から５００℃まで昇温し、重量減少率１０％（重量が１０質量％減少すること）となる温度を測定した。 <10% Weight Loss Temperature>
The 10% weight loss temperature of fatty acids 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 raised from 40° C. to 500° C. at a heating rate of 10° C./min, and the temperature at which the weight reduction rate was 10% (10% by mass reduction) was measured.
（原材料）
実施例及び比較例で使用した化合物の略号は以下の通りである。
ＭＭＡ：メチルメタクリレート（商品名：アクリエステル（登録商標）Ｍ、三菱ケミカル（株）製）
ＭＡ：アクリル酸メチル（三菱ケミカル（株）製）
ＭＡＡ：メタクリル酸
重合開始剤（１）：２，２’－アゾビス（２－メチルプロピオンアミジン）二塩酸塩
重合開始剤（２）：２，２’－アゾビス－２－メチルブチロニトリル（商品名：Ｖ－５９、和光純薬工業（株）製）
連鎖移動剤（１）：ｎ－オクチルメルカプタン（東京化成工業（株）製）
重合体（１）：アクリペット（登録商標）ＶＨ（商品名、三菱ケミカル（株）製、メチルメタクリレート単位を９８質量％含むアクリル樹脂）
重合体（２）：製造例１で製造したメタクリル系重合体
脂肪酸化合物（Ｂ－１）：ミリスチン酸（商品名：ルナックＭＹ-９８、花王社製）
脂肪酸化合物（Ｂ－２）：パルミチン酸（商品名：ルナックＰ-９５、花王社製）
脂肪酸化合物（Ｂ－３）：ステアリン酸（商品名：ルナックＳ-９８、花王社製）
脂肪酸化合物（Ｂ－４）：ミリスチルアルコール（商品名：カルコール４０９８、花王社製）
脂肪酸化合物（Ｂ－５）：セチルアルコール（商品名：カルコール６０９８、花王社製）
脂肪酸化合物（Ｂ－６）：ステアリルアルコール（商品名：カルコール８０９８、花王社製）
脂肪酸化合物（Ｂ－７）：グリセリンモノステアレート（商品名：リケマールＳ１００Ａ、理研ビタミン社製）
脂肪酸化合物（Ｂ－８）：グリセリンモノ・ジステアレート（商品名：リケマールＳ２００Ａ、理研ビタミン社製）
脂肪酸化合物（Ｂ－９）：ステアリルステアレート（商品名：リケマールＳＬ―９００Ａ、理研ビタミン社製）
脂肪酸化合物（Ｂ－１０）：ステアリン酸アミド（商品名：脂肪酸アマイドＳ、花王社製） (raw materials)
The abbreviations of the compounds used in Examples and Comparative Examples are as follows.
MMA: Methyl methacrylate (trade name: Acryester (registered trademark) M, manufactured by Mitsubishi Chemical Corporation)
MA: Methyl acrylate (manufactured by Mitsubishi Chemical Corporation)
MAA: methacrylic acid polymerization initiator (1): 2,2'-azobis (2-methylpropionamidine) dihydrochloride polymerization initiator (2): 2,2'-azobis-2-methylbutyronitrile (trade name : V-59, manufactured by Wako Pure Chemical Industries, Ltd.)
Chain transfer agent (1): n-octyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.)
Polymer (1): ACRYPET (registered trademark) VH (trade name, manufactured by Mitsubishi Chemical Corporation, acrylic resin containing 98% by mass of methyl methacrylate units)
Polymer (2): Methacrylic polymer fatty acid compound (B-1) produced in Production Example 1: Myristic acid (trade name: LUNAC MY-98, manufactured by Kao Corporation)
Fatty acid compound (B-2): palmitic acid (trade name: LUNAC P-95, manufactured by Kao Corporation)
Fatty acid compound (B-3): stearic acid (trade name: Lunax S-98, manufactured by Kao Corporation)
Fatty acid compound (B-4): myristyl alcohol (trade name: Calcol 4098, manufactured by Kao Corporation)
Fatty acid compound (B-5): cetyl alcohol (trade name: Calcol 6098, manufactured by Kao Corporation)
Fatty acid compound (B-6): stearyl alcohol (trade name: Calcol 8098, manufactured by Kao Corporation)
Fatty acid compound (B-7): glycerin monostearate (trade name: Rikemar S100A, manufactured by Riken Vitamin Co., Ltd.)
Fatty acid compound (B-8): glycerin mono-distearate (trade name: Rikemar S200A, manufactured by Riken Vitamin Co., Ltd.)
Fatty acid compound (B-9): stearyl stearate (trade name: Rikemar SL-900A, manufactured by Riken Vitamin Co., Ltd.)
Fatty acid compound (B-10): stearic acid amide (trade name: fatty acid amide S, manufactured by Kao Corporation)
実施例及び比較例で使用した化合物の略号は以下の通りである。
ＭＭＡ：メチルメタクリレート（商品名：アクリエステル（登録商標）Ｍ、三菱ケミカル（株）製）
ＭＡ：アクリル酸メチル（三菱ケミカル（株）製）
ＭＡＡ：メタクリル酸
重合開始剤（１）：２，２’－アゾビス（２－メチルプロピオンアミジン）二塩酸塩
重合開始剤（２）：２，２’－アゾビス－２－メチルブチロニトリル（商品名：Ｖ－５９、和光純薬工業（株）製）
連鎖移動剤（１）：ｎ－オクチルメルカプタン（東京化成工業（株）製）
重合体（１）：アクリペット（登録商標）ＶＨ（商品名、三菱ケミカル（株）製、メチルメタクリレート単位を９８質量％含むアクリル樹脂）
重合体（２）：製造例１で製造したメタクリル系重合体
脂肪酸化合物（Ｂ－１）：ミリスチン酸（商品名：ルナックＭＹ-９８、花王社製）
脂肪酸化合物（Ｂ－２）：パルミチン酸（商品名：ルナックＰ-９５、花王社製）
脂肪酸化合物（Ｂ－３）：ステアリン酸（商品名：ルナックＳ-９８、花王社製）
脂肪酸化合物（Ｂ－４）：ミリスチルアルコール（商品名：カルコール４０９８、花王社製）
脂肪酸化合物（Ｂ－５）：セチルアルコール（商品名：カルコール６０９８、花王社製）
脂肪酸化合物（Ｂ－６）：ステアリルアルコール（商品名：カルコール８０９８、花王社製）
脂肪酸化合物（Ｂ－７）：グリセリンモノステアレート（商品名：リケマールＳ１００Ａ、理研ビタミン社製）
脂肪酸化合物（Ｂ－８）：グリセリンモノ・ジステアレート（商品名：リケマールＳ２００Ａ、理研ビタミン社製）
脂肪酸化合物（Ｂ－９）：ステアリルステアレート（商品名：リケマールＳＬ―９００Ａ、理研ビタミン社製）
脂肪酸化合物（Ｂ－１０）：ステアリン酸アミド（商品名：脂肪酸アマイドＳ、花王社製） (raw materials)
The abbreviations of the compounds used in Examples and Comparative Examples are as follows.
MMA: Methyl methacrylate (trade name: Acryester (registered trademark) M, manufactured by Mitsubishi Chemical Corporation)
MA: Methyl acrylate (manufactured by Mitsubishi Chemical Corporation)
MAA: methacrylic acid polymerization initiator (1): 2,2'-azobis (2-methylpropionamidine) dihydrochloride polymerization initiator (2): 2,2'-azobis-2-methylbutyronitrile (trade name : V-59, manufactured by Wako Pure Chemical Industries, Ltd.)
Chain transfer agent (1): n-octyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.)
Polymer (1): ACRYPET (registered trademark) VH (trade name, manufactured by Mitsubishi Chemical Corporation, acrylic resin containing 98% by mass of methyl methacrylate units)
Polymer (2): Methacrylic polymer fatty acid compound (B-1) produced in Production Example 1: Myristic acid (trade name: LUNAC MY-98, manufactured by Kao Corporation)
Fatty acid compound (B-2): palmitic acid (trade name: LUNAC P-95, manufactured by Kao Corporation)
Fatty acid compound (B-3): stearic acid (trade name: Lunax S-98, manufactured by Kao Corporation)
Fatty acid compound (B-4): myristyl alcohol (trade name: Calcol 4098, manufactured by Kao Corporation)
Fatty acid compound (B-5): cetyl alcohol (trade name: Calcol 6098, manufactured by Kao Corporation)
Fatty acid compound (B-6): stearyl alcohol (trade name: Calcol 8098, manufactured by Kao Corporation)
Fatty acid compound (B-7): glycerin monostearate (trade name: Rikemar S100A, manufactured by Riken Vitamin Co., Ltd.)
Fatty acid compound (B-8): glycerin mono-distearate (trade name: Rikemar S200A, manufactured by Riken Vitamin Co., Ltd.)
Fatty acid compound (B-9): stearyl stearate (trade name: Rikemar SL-900A, manufactured by Riken Vitamin Co., Ltd.)
Fatty acid compound (B-10): stearic acid amide (trade name: fatty acid amide S, manufactured by Kao Corporation)
［製造例１］
脱イオン水９００質量部、メタクリル酸２－スルホエチルナトリウム６０質量部、メタクリル酸カリウム１０質量部及びＭＭＡ１２質量部を、内部を窒素置換した還流冷却器付き反応容器に加えた後、撹拌しながら反応容器内の液温が５０℃になるように昇温した。その後、重合開始剤（１）０．０８質量部を加え、撹拌しながら反応容器内の液温が６０℃になるように昇温した後、滴下ポンプを用いて、ＭＭＡを０．２４質量部／分の速度で７５分間かけて連続的に滴下した。その後、さらに６時間保持して重合を行ない、分散剤（固形分１０質量％）を得た。 [Production Example 1]
900 parts by mass of deionized water, 60 parts by mass of 2-sulfoethylsodium methacrylate, 10 parts by mass of potassium methacrylate and 12 parts by mass of MMA were added to a reaction vessel equipped with a reflux condenser whose interior was replaced with nitrogen, and then the reaction was carried out with stirring. The temperature of the liquid in the container was raised to 50°C. After that, 0.08 part by mass of polymerization initiator (1) was added, and the liquid temperature in the reaction vessel was raised to 60° C. while stirring, and then 0.24 part by mass of MMA was added using a dropping pump. /min over a period of 75 minutes. After that, polymerization was carried out by holding for another 6 hours to obtain a dispersant (solid content: 10% by mass).
脱イオン水９００質量部、メタクリル酸２－スルホエチルナトリウム６０質量部、メタクリル酸カリウム１０質量部及びＭＭＡ１２質量部を、内部を窒素置換した還流冷却器付き反応容器に加えた後、撹拌しながら反応容器内の液温が５０℃になるように昇温した。その後、重合開始剤（１）０．０８質量部を加え、撹拌しながら反応容器内の液温が６０℃になるように昇温した後、滴下ポンプを用いて、ＭＭＡを０．２４質量部／分の速度で７５分間かけて連続的に滴下した。その後、さらに６時間保持して重合を行ない、分散剤（固形分１０質量％）を得た。 [Production Example 1]
900 parts by mass of deionized water, 60 parts by mass of 2-sulfoethylsodium methacrylate, 10 parts by mass of potassium methacrylate and 12 parts by mass of MMA were added to a reaction vessel equipped with a reflux condenser whose interior was replaced with nitrogen, and then the reaction was carried out with stirring. The temperature of the liquid in the container was raised to 50°C. After that, 0.08 part by mass of polymerization initiator (1) was added, and the liquid temperature in the reaction vessel was raised to 60° C. while stirring, and then 0.24 part by mass of MMA was added using a dropping pump. /min over a period of 75 minutes. After that, polymerization was carried out by holding for another 6 hours to obtain a dispersant (solid content: 10% by mass).
脱イオン水２０００質量部及び硫酸ナトリウム４．２質量部を、窒素ガス導入管を備えた還流冷却器付き反応容器に加えた後、３２０ｒｐｍの撹拌速度で１５分間撹拌した。その後、ＭＭＡ１３５１．６質量部、ＭＡＡ３６．３質量部、ＭＡ１２．１質量部、重合開始剤（２）を２．８質量部及び連鎖移動剤（１）４．２質量部の混合溶液を反応容器に加え、５分間撹拌した。次いで、製造例１で製造した分散剤（固形分１０質量％）６．７２質量部を反応容器に加えた後、撹拌して、反応容器中の単量体組成物を水中に分散させた。その後、反応容器内を窒素置換した。
After adding 2000 parts by mass of deionized water and 4.2 parts by mass of sodium sulfate to a reaction vessel equipped with a nitrogen gas inlet tube and equipped with a reflux condenser, the mixture was stirred at a stirring speed of 320 rpm for 15 minutes. After that, a mixed solution of 1351.6 parts by mass of MMA, 36.3 parts by mass of MAA, 12.1 parts by mass of MA, 2.8 parts by mass of polymerization initiator (2) and 4.2 parts by mass of chain transfer agent (1) was added to a reaction vessel. and stirred for 5 minutes. Then, 6.72 parts by mass of the dispersant (solid content: 10% by mass) produced in Production Example 1 was added to the reaction vessel and stirred to disperse the monomer composition in the reaction vessel in water. After that, the inside of the reaction vessel was replaced with nitrogen.
次いで、反応容器内の液温が７５℃になるように昇温した後、さらに反応容器内の液温を連続的に測定して重合発熱ピークが観測されるまで７５℃を保持した。重合発熱ピークが観測された後、反応容器内の液温が９０℃になるように昇温した後、６０分間保持して、重合を行なった。その後、反応容器内の混合物を濾過し、濾過物を脱イオン水で洗浄し、８０℃で１６時間乾燥し、ビーズ状の共重合体を得て、これをメタクリル系樹脂の前駆体（共重合体前駆体（１））とした。
共重合体前駆体（１）の組成は、上述した「単位（Ａ）、（Ｂ）及び（Ｃ）の含有率」の測定方法に準じで分析したところ、ＭＭＡ単位９６．０ｍｏｌ％、メタクリル酸由来の繰り返し単位（以下、「ＭＡＡ単位」という。）３．０ｍｏｌ％、アクリル酸メチル由来の繰り返し単位（以下、「ＭＡ単位」という。）１．０ｍｏｌ％であった。 Then, after the temperature of the liquid in the reaction vessel was raised to 75° C., the temperature of the liquid in the reaction vessel was continuously measured and kept at 75° C. until the polymerization exothermic peak was observed. After the polymerization exothermic peak was observed, the temperature of the liquid in the reaction vessel was raised to 90° C., and the mixture was held for 60 minutes to carry out polymerization. After that, the mixture in the reaction vessel is filtered, and the filtrate is washed with deionized water and dried at 80° C. for 16 hours to obtain a bead-like copolymer, which is used as a methacrylic resin precursor (copolymer). A combined precursor (1)) was obtained.
The composition of the copolymer precursor (1) was analyzed according to the above-described measurement method for the "content of units (A), (B) and (C)", and found to be 96.0 mol% of MMA units and methacrylic acid. 3.0 mol % of repeating units (hereinafter referred to as "MAA units") derived from methyl acrylate and 1.0 mol % of repeating units (hereinafter referred to as "MA units") derived from methyl acrylate.
共重合体前駆体（１）の組成は、上述した「単位（Ａ）、（Ｂ）及び（Ｃ）の含有率」の測定方法に準じで分析したところ、ＭＭＡ単位９６．０ｍｏｌ％、メタクリル酸由来の繰り返し単位（以下、「ＭＡＡ単位」という。）３．０ｍｏｌ％、アクリル酸メチル由来の繰り返し単位（以下、「ＭＡ単位」という。）１．０ｍｏｌ％であった。 Then, after the temperature of the liquid in the reaction vessel was raised to 75° C., the temperature of the liquid in the reaction vessel was continuously measured and kept at 75° C. until the polymerization exothermic peak was observed. After the polymerization exothermic peak was observed, the temperature of the liquid in the reaction vessel was raised to 90° C., and the mixture was held for 60 minutes to carry out polymerization. After that, the mixture in the reaction vessel is filtered, and the filtrate is washed with deionized water and dried at 80° C. for 16 hours to obtain a bead-like copolymer, which is used as a methacrylic resin precursor (copolymer). A combined precursor (1)) was obtained.
The composition of the copolymer precursor (1) was analyzed according to the above-described measurement method for the "content of units (A), (B) and (C)", and found to be 96.0 mol% of MMA units and methacrylic acid. 3.0 mol % of repeating units (hereinafter referred to as "MAA units") derived from methyl acrylate and 1.0 mol % of repeating units (hereinafter referred to as "MA units") derived from methyl acrylate.
共重合体前駆体（１）を二軸押出機（機種名「ＰＣＭ３０」、（株）池貝製）に供給し、２５０℃で混練し、ペレット状のメタクリル系重合体を得て、これを重合体（２）とした。
得られた重合体（２）の組成は、ＭＭＡ単位９７．００ｍｏｌ％、（メタ）アクリル酸単位２．９９ｍｏｌ％、グルタル酸無水物構造単位０．０１ｍｏｌ％であった。なお、（メタ）アクリル酸単位には、ＭＡＡ単位及びＭＡ単位を含む。 The copolymer precursor (1) is supplied to a twin-screw extruder (model name “PCM30”, manufactured by Ikegai Co., Ltd.) and kneaded at 250° C. to obtain a pellet-shaped methacrylic polymer, which is then weighed. Combined (2).
The composition of the obtained polymer (2) was 97.00 mol % of MMA units, 2.99 mol % of (meth)acrylic acid units, and 0.01 mol % of glutaric anhydride structural units. The (meth)acrylic acid units include MAA units and MA units.
得られた重合体（２）の組成は、ＭＭＡ単位９７．００ｍｏｌ％、（メタ）アクリル酸単位２．９９ｍｏｌ％、グルタル酸無水物構造単位０．０１ｍｏｌ％であった。なお、（メタ）アクリル酸単位には、ＭＡＡ単位及びＭＡ単位を含む。 The copolymer precursor (1) is supplied to a twin-screw extruder (model name “PCM30”, manufactured by Ikegai Co., Ltd.) and kneaded at 250° C. to obtain a pellet-shaped methacrylic polymer, which is then weighed. Combined (2).
The composition of the obtained polymer (2) was 97.00 mol % of MMA units, 2.99 mol % of (meth)acrylic acid units, and 0.01 mol % of glutaric anhydride structural units. The (meth)acrylic acid units include MAA units and MA units.
［実施例１］
重合体（１）１００質量部、脂肪酸として脂肪酸化合物（Ｂ－１）０．１質量部を、二軸押出機（機種名「ＴＥＭ３５」、芝浦機械（株）製）に供給し、押出機のシリンダー温度２５０℃で溶融混練し、金型温度６０℃でペレット状のメタクリル系樹脂組成物を得た。
得られたメタクリル系樹脂組成物の評価結果を、表１に示す。 [Example 1]
100 parts by mass of polymer (1) and 0.1 part by mass of fatty acid compound (B-1) as fatty acid are supplied to a twin-screw extruder (model name “TEM35”, manufactured by Shibaura Machine Co., Ltd.), and the extruder Melt-kneading was carried out at a cylinder temperature of 250°C, and a pellet-shaped methacrylic resin composition was obtained at a mold temperature of 60°C.
Table 1 shows the evaluation results of the obtained methacrylic resin composition.
重合体（１）１００質量部、脂肪酸として脂肪酸化合物（Ｂ－１）０．１質量部を、二軸押出機（機種名「ＴＥＭ３５」、芝浦機械（株）製）に供給し、押出機のシリンダー温度２５０℃で溶融混練し、金型温度６０℃でペレット状のメタクリル系樹脂組成物を得た。
得られたメタクリル系樹脂組成物の評価結果を、表１に示す。 [Example 1]
100 parts by mass of polymer (1) and 0.1 part by mass of fatty acid compound (B-1) as fatty acid are supplied to a twin-screw extruder (model name “TEM35”, manufactured by Shibaura Machine Co., Ltd.), and the extruder Melt-kneading was carried out at a cylinder temperature of 250°C, and a pellet-shaped methacrylic resin composition was obtained at a mold temperature of 60°C.
Table 1 shows the evaluation results of the obtained methacrylic resin composition.
［参考例１］
脂肪酸を使用しなかった以外は、実施例１と同様に操作を行い、ペレット状のメタクリル系樹脂組成物を得た。
得られたメタクリル系樹脂組成物の評価結果を、表１に示す。 [Reference example 1]
A methacrylic resin composition in the form of pellets was obtained in the same manner as in Example 1, except that no fatty acid was used.
Table 1 shows the evaluation results of the obtained methacrylic resin composition.
脂肪酸を使用しなかった以外は、実施例１と同様に操作を行い、ペレット状のメタクリル系樹脂組成物を得た。
得られたメタクリル系樹脂組成物の評価結果を、表１に示す。 [Reference example 1]
A methacrylic resin composition in the form of pellets was obtained in the same manner as in Example 1, except that no fatty acid was used.
Table 1 shows the evaluation results of the obtained methacrylic resin composition.
［実施例２～３、比較例１～７］
脂肪酸化合物の種類を変更した以外は、実施例１と同様に操作を行い、ペレット状のメタクリル系樹脂組成物を得た。
得られたメタクリル系樹脂組成物の評価結果を、表１に示す。 [Examples 2-3, Comparative Examples 1-7]
A methacrylic resin composition in the form of pellets was obtained in the same manner as in Example 1, except that the type of fatty acid compound was changed.
Table 1 shows the evaluation results of the obtained methacrylic resin composition.
脂肪酸化合物の種類を変更した以外は、実施例１と同様に操作を行い、ペレット状のメタクリル系樹脂組成物を得た。
得られたメタクリル系樹脂組成物の評価結果を、表１に示す。 [Examples 2-3, Comparative Examples 1-7]
A methacrylic resin composition in the form of pellets was obtained in the same manner as in Example 1, except that the type of fatty acid compound was changed.
Table 1 shows the evaluation results of the obtained methacrylic resin composition.
［実施例４、比較例８～９］
重合体（１）の代わりに重合体（２）を用いて、脂肪酸化合物の種類と添加量を変更した以外は、実施例１と同様に操作を行い、ペレット状のメタクリル系樹脂組成物を得た。
得られたメタクリル系樹脂組成物の評価結果を、表１に示す。 [Example 4, Comparative Examples 8 to 9]
A methacrylic resin composition in the form of pellets was obtained in the same manner as in Example 1, except that the polymer (2) was used instead of the polymer (1) and the type and amount of the fatty acid compound added were changed. rice field.
Table 1 shows the evaluation results of the obtained methacrylic resin composition.
重合体（１）の代わりに重合体（２）を用いて、脂肪酸化合物の種類と添加量を変更した以外は、実施例１と同様に操作を行い、ペレット状のメタクリル系樹脂組成物を得た。
得られたメタクリル系樹脂組成物の評価結果を、表１に示す。 [Example 4, Comparative Examples 8 to 9]
A methacrylic resin composition in the form of pellets was obtained in the same manner as in Example 1, except that the polymer (2) was used instead of the polymer (1) and the type and amount of the fatty acid compound added were changed. rice field.
Table 1 shows the evaluation results of the obtained methacrylic resin composition.
実施例１～４の樹脂成形体は、射出成形時の離形性、及び熱板融着性に優れていた。
参考例１の樹脂成形体は、脂肪酸を含有していないため、射出成形時の離形性、及び熱板融着性に劣っていた。
比較例１～９の樹脂成形体は、脂肪酸化合物を含むが、脂肪酸を用いていないため、射出成形時の離形性、及び熱板融着性に劣っていた。 The resin moldings of Examples 1 to 4 were excellent in releasability during injection molding and hot plate fusion bonding.
Since the resin molding of Reference Example 1 did not contain fatty acid, it was inferior in releasability during injection molding and hot plate fusion bonding.
Although the resin moldings of Comparative Examples 1 to 9 contained a fatty acid compound, they were inferior in releasability during injection molding and hot plate fusion bonding since no fatty acid was used.
参考例１の樹脂成形体は、脂肪酸を含有していないため、射出成形時の離形性、及び熱板融着性に劣っていた。
比較例１～９の樹脂成形体は、脂肪酸化合物を含むが、脂肪酸を用いていないため、射出成形時の離形性、及び熱板融着性に劣っていた。 The resin moldings of Examples 1 to 4 were excellent in releasability during injection molding and hot plate fusion bonding.
Since the resin molding of Reference Example 1 did not contain fatty acid, it was inferior in releasability during injection molding and hot plate fusion bonding.
Although the resin moldings of Comparative Examples 1 to 9 contained a fatty acid compound, they were inferior in releasability during injection molding and hot plate fusion bonding since no fatty acid was used.
本発明の熱板融着用メタクリル系樹脂組成物は、熱板融着時に熱板から樹脂組成物を引き離す際に糸曳きを生じにくく、熱板融着性に優れている。また、射出成形時に金型表面に樹脂組成物の剥離残渣が生じにくく、金型からの離形性に優れる。そのため、本発明の熱板融着用メタクリル系樹脂組成物を含む成形体は、テールランプカバーや、ヘッドランプカバー、メーターパネルといった車両の内外装材料等の車両用部材；建築部材；洗面化粧台、浴槽、水洗便器等の住宅設備向け部材の原材料に好適に用いることができ、特に、車両用部材の原材料に好適である。
The methacrylic resin composition for hot plate welding of the present invention is less likely to cause stringing when the resin composition is separated from the hot plate during hot plate welding, and has excellent hot plate welding properties. In addition, the resin composition is less likely to leave a peeling residue on the surface of the mold during injection molding, and is excellent in releasability from the mold. Therefore, the molded article containing the methacrylic resin composition for hot plate welding of the present invention can be used as a vehicle member such as a tail lamp cover, a head lamp cover, and a meter panel such as a vehicle interior and exterior material; a building member; It can be suitably used as a raw material for housing equipment members such as flush toilets, and is particularly suitable as a raw material for vehicle members.
車両用部品としては、例えば、テールランプカバー、ヘッドランプカバー、メーターパネル、ドアミラーハウジング、ピラーカバー（サッシュカバー）、ライセンスガーニッシュ、フロントグリル、フォグガーニッシュ、エンブレム等が挙げられる。
Examples of vehicle parts include tail lamp covers, head lamp covers, meter panels, door mirror housings, pillar covers (sash covers), license garnishes, front grills, fog garnishes, and emblems.
１ 第１の部材
１ａ 第１の部材の溶融部
２ 第２の部材
２ａ 第２の部材の溶融部
３ 熱板
４ 円盤状の成形品
５ スプルー部
６ 円錐状の試験片
７ ホットプレート
８ 熱板
９ 底面部
１０ 試験片と熱板との間に生じた糸曳き 1 First member 1a First member meltedportion 2 Second member 2a Second member melted portion 3 Hot plate 4 Disk-shaped molded product 5 Sprue portion 6 Conical test piece 7 Hot plate 8 Hot plate 9 Bottom part 10 Stringing generated between the test piece and the hot plate
１ａ 第１の部材の溶融部
２ 第２の部材
２ａ 第２の部材の溶融部
３ 熱板
４ 円盤状の成形品
５ スプルー部
６ 円錐状の試験片
７ ホットプレート
８ 熱板
９ 底面部
１０ 試験片と熱板との間に生じた糸曳き 1 First member 1a First member melted
Claims (17)
- メタクリル系重合体及び脂肪酸を含む、熱板融着用メタクリル系樹脂組成物。 A methacrylic resin composition for hot plate welding containing a methacrylic polymer and a fatty acid.
- 前記脂肪酸の炭素数が１０～２２である、請求項１に記載の熱板融着用メタクリル系樹脂組成物。 The methacrylic resin composition for hot plate welding according to claim 1, wherein the fatty acid has 10 to 22 carbon atoms.
- 前記脂肪酸の１０％重量減少温度が２５０℃以下である、請求項１又は２に記載の熱板融着用メタクリル系樹脂組成物。 The methacrylic resin composition for hot plate welding according to claim 1 or 2, wherein the 10% weight loss temperature of the fatty acid is 250°C or less.
- 前記脂肪酸の融点が５０℃以上である、請求項１～３のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物。 The methacrylic resin composition for hot plate welding according to any one of claims 1 to 3, wherein the fatty acid has a melting point of 50°C or higher.
- 前記脂肪酸が分子内にカルボキシル基を少なくとも１個有する鎖状炭化水素化合物である、請求項１～４のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物。 The methacrylic resin composition for hot plate bonding according to any one of claims 1 to 4, wherein the fatty acid is a chain hydrocarbon compound having at least one carboxyl group in the molecule.
- 前記脂肪酸の分子量が１００～５００である、請求項１～５のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物。 The methacrylic resin composition for hot plate welding according to any one of claims 1 to 5, wherein the fatty acid has a molecular weight of 100 to 500.
- 前記メタクリル系重合体１００質量部に対して、前記脂肪酸の含有量が０．０１～１質量部である、請求項１～６のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物。 The methacrylic resin composition for hot plate welding according to any one of claims 1 to 6, wherein the content of the fatty acid is 0.01 to 1 part by mass with respect to 100 parts by mass of the methacrylic polymer. .
- 熱板融着用メタクリル系樹脂組成物の総質量（１００質量％）に対して、前記脂肪酸の含有割合が０．０１～１質量％である、請求項１～６のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物。 7. The content ratio of the fatty acid is 0.01 to 1% by mass with respect to the total mass (100% by mass) of the methacrylic resin composition for hot plate welding, according to any one of claims 1 to 6. A methacrylic resin composition for hot plate welding.
- 前記脂肪酸が、ステアリン酸、パルミチン酸、及びミリスチン酸から選ばれる少なくとも１種を含む、請求項１～８のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物。 The methacrylic resin composition for hot plate bonding according to any one of claims 1 to 8, wherein the fatty acid contains at least one selected from stearic acid, palmitic acid, and myristic acid.
- 前記メタクリル系重合体がメタクリル酸メチル由来の繰り返し単位を含み、前記メタクリル系重合体中の前記メタクリル酸メチル由来の繰り返し単位の含有割合が７０質量％以上である、請求項１～９のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物。 Any one of claims 1 to 9, wherein the methacrylic polymer contains repeating units derived from methyl methacrylate, and the content of the repeating units derived from methyl methacrylate in the methacrylic polymer is 70% by mass or more. 1. The methacrylic resin composition for hot plate welding according to item 1.
- 前記メタクリル系重合体が、（メタ）アクリル酸エステル単量体由来の繰り返し単位及び環構造由来の構造単位を含む重合体（Ａ）であり、
前記環構造由来の構造単位が、グルタル酸無水物構造単位、マレイン酸無水物構造単位、グルタルイミド構造単位、ラクトン環構造単位、及びＮ－置換マレイミド構造単位から選ばれる少なくとも１種を含む、請求項１～１０のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物。 The methacrylic polymer is a polymer (A) containing a repeating unit derived from a (meth)acrylate monomer and a structural unit derived from a ring structure,
wherein the structural unit derived from the ring structure comprises at least one selected from a glutaric anhydride structural unit, a maleic anhydride structural unit, a glutarimide structural unit, a lactone ring structural unit, and an N-substituted maleimide structural unit; Item 11. The methacrylic resin composition for hot plate welding according to any one of items 1 to 10. - 前記重合体（Ａ）が、メタクリル酸メチル由来の繰り返し単位（Ａ１）、（メタ）アクリル酸由来の繰り返し単位（Ａ２）、及びグルタル酸無水物構造単位（Ａ３）を含む、請求項１１に記載の熱板融着用メタクリル系樹脂組成物。 12. The polymer (A) according to claim 11, wherein the polymer (A) comprises a repeating unit (A1) derived from methyl methacrylate, a repeating unit (A2) derived from (meth)acrylic acid, and a glutaric anhydride structural unit (A3). A methacrylic resin composition for hot plate welding.
- 車両用部材の原材料として用いる、請求項１～１２のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物。 The methacrylic resin composition for hot plate welding according to any one of claims 1 to 12, which is used as a raw material for vehicle members.
- 前記車両用部材が、テールランプカバー、ヘッドランプカバー、及びメーターパネルから選ばれる少なくとも１種である、請求項１３に記載の熱板融着用メタクリル系樹脂組成物。 The methacrylic resin composition for hot plate bonding according to claim 13, wherein the vehicle member is at least one selected from a tail lamp cover, a head lamp cover, and a meter panel.
- 請求項１～１４のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物の熱板融着への使用。 Use of the methacrylic resin composition for hot plate welding according to any one of claims 1 to 14 for hot plate welding.
- 請求項１～１４のいずれか一項に記載の熱板融着用メタクリル系樹脂組成物から形成された第１の部材の少なくとも一部を熱板に接触させて溶融させる工程と、
前記第１の部材を前記熱板から引き離し、第２の部材と圧着する工程と、を備える、第１の部材と第２の部材の融着方法。 a step of bringing at least part of the first member formed from the methacrylic resin composition for hot plate welding according to any one of claims 1 to 14 into contact with a hot plate to melt the first member;
pulling the first member away from the hot plate and crimping the first member to a second member. - 第１の部材と第２の部材とを接着してなる複合部材を含む車両用部材であって、
前記第１の部材が、メタクリル系重合体及び脂肪酸を含む、車両用部材。 A vehicle member including a composite member formed by bonding a first member and a second member,
A vehicle member, wherein the first member contains a methacrylic polymer and a fatty acid.
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| KR1020237029842A KR20230142560A (en) | 2021-03-09 | 2022-03-01 | Methacrylic resin composition for hot plate fusion, use of methacrylic resin composition for hot plate fusion in hot plate fusion, fusion method, and vehicle member |
| JP2023505318A JPWO2022190951A1 (en) | 2021-03-09 | 2022-03-01 | |
| CN202280018609.4A CN116964146A (en) | 2021-03-09 | 2022-03-01 | Methacrylic resin composition for hot plate welding, use of methacrylic resin composition for hot plate welding in hot plate welding, welding method, and vehicle member |
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| JP2021036914A JP7136249B1 (en) | 2021-03-09 | 2021-03-09 | METHACRYLIC RESIN COMPOSITION FOR HOT PLATE FUSION AND USE AND METHOD FOR HOT PLATE FUSION |
| JP2021-036914 | 2021-03-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08302145A (en) * | 1995-05-08 | 1996-11-19 | Asahi Chem Ind Co Ltd | Methacrylic resin composition and optical part produced therefrom |
| JP2009249529A (en) * | 2008-04-08 | 2009-10-29 | Sumitomo Chemical Co Ltd | Methacrylic resin composition for hot plate melt-bonding |
| JP2011168683A (en) * | 2010-02-18 | 2011-09-01 | Asahi Kasei Chemicals Corp | Methacrylic resin composition and method for producing the same |
| JP2018162406A (en) * | 2017-03-27 | 2018-10-18 | 三菱ケミカル株式会社 | Resin composition, method for producing resin composition, molded body and component for vehicle |
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| JP4977294B2 (en) * | 2001-06-29 | 2012-07-18 | 日本エイアンドエル株式会社 | Hot plate fusion resin composition and lamp housing molded article for vehicle lamp |
| JP4777617B2 (en) | 2004-02-25 | 2011-09-21 | 日本エイアンドエル株式会社 | Hot plate fusion resin composition and lamp housing molded article for vehicle lamp |
| JP5568840B2 (en) | 2008-04-08 | 2014-08-13 | 住友化学株式会社 | Methacrylic resin composition for hot plate fusion |
| JP5642979B2 (en) * | 2010-02-16 | 2014-12-17 | 旭化成ケミカルズ株式会社 | Methacrylic resin composition |
| JP6522288B2 (en) * | 2014-06-23 | 2019-05-29 | 住友化学株式会社 | Methacrylic resin composition and molded article thereof |
| JP7136249B1 (en) * | 2021-03-09 | 2022-09-13 | 三菱ケミカル株式会社 | METHACRYLIC RESIN COMPOSITION FOR HOT PLATE FUSION AND USE AND METHOD FOR HOT PLATE FUSION |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08302145A (en) * | 1995-05-08 | 1996-11-19 | Asahi Chem Ind Co Ltd | Methacrylic resin composition and optical part produced therefrom |
| JP2009249529A (en) * | 2008-04-08 | 2009-10-29 | Sumitomo Chemical Co Ltd | Methacrylic resin composition for hot plate melt-bonding |
| JP2011168683A (en) * | 2010-02-18 | 2011-09-01 | Asahi Kasei Chemicals Corp | Methacrylic resin composition and method for producing the same |
| JP2018162406A (en) * | 2017-03-27 | 2018-10-18 | 三菱ケミカル株式会社 | Resin composition, method for producing resin composition, molded body and component for vehicle |
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| JP2022137415A (en) | 2022-09-22 |
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| JP7136249B1 (en) | 2022-09-13 |
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