Classifications

• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/48—Separation; Purification; Stabilisation; Use of additives
  • C07C67/62—Use of additives, e.g. for stabilisation
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/02—Polymerisation in bulk
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • 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
  • C08K5/01—Hydrocarbons
• • 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
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

• the present invention relates to a monomer composition, a resin composition, a method for producing a resin composition, a resin molded body, and a method for producing a resin molded body.
• Methacrylic resins have excellent transparency, heat resistance, and weather resistance, and also have well-balanced performance in terms of resin properties such as mechanical strength, thermal properties, and moldability. Due to these excellent characteristics, they are used in many applications such as vehicle parts, medical parts, toys, liquid containers, optical materials, signs, displays, decorative parts, architectural parts, and electronic device faceplates, and are particularly used in translucent parts.
• Patent Document 1 discloses a methacrylic resin obtained by polymerizing a monomer such as methyl methacrylate in the presence of a hindered amine compound with a specific structure, which is a type of light stabilizer.
• Patent Document 2 discloses a methacrylic resin that includes a polymer having a triazine compound as a structural unit.
• the object of the present invention is to provide a monomer composition, a resin composition, a method for producing a resin composition, a resin molded body, and a method for producing a resin molded body, which are capable of obtaining a resin composition having excellent light stability while maintaining the inherent transparency and heat resistance of methacrylic resins.
• the present invention has the following features:
• a monomer composition comprising methyl methacrylate, an ⁇ -olefin, and methyl isobutyrate, The content of the methyl isobutyrate is more than 260 ppm by mass, based on the total mass of the monomer composition;
• the monomer composition according to [1] wherein the content of the methyl methacrylate is 85% by mass or more based on the total mass of the monomer composition.
• a method for producing a resin composition comprising: a radical polymerization step of radically polymerizing a polymerizable composition containing the monomer composition according to any one of [1] to [18].
• a resin composition comprising a polymer of the monomer composition according to any one of [1] to [18].
• a resin composition comprising a methacrylic polymer (P), an ⁇ -olefin, and methyl isobutyrate, The content of the methyl isobutyrate is more than 49 ppm by mass relative to the total mass of the resin composition,
• the methacrylic polymer (P) contains 50 mass% or more of repeating units derived from methyl methacrylate, based on the total mass of the methacrylic polymer (P).
• a resin molded product comprising the resin composition according to any one of [20] to [34].
• a vehicle member comprising the resin molded article according to [35].
• a medical device comprising the resin molded article according to [35].
• a toy comprising the resin molded article according to [35].
• a liquid container comprising the resin molded article according to [35].
• An optical material comprising the resin molded article according to [35].
• a signboard comprising the resin molding according to [35].
• a display comprising the resin molded article according to [35].
• the method includes a molding step of molding a resin composition containing a methacrylic polymer (P), an ⁇ -olefin, and methyl isobutyrate,
• the content of the methyl isobutyrate in the resin composition is more than 49 ppm by mass relative to the total mass of the resin composition;
• the method for producing a resin molded article, wherein the ⁇ -olefin comprises at least one selected from the group consisting of 2-ethyl-1-hexene, 1-octene, and 1-dodecene.
• the present invention provides a monomer composition, a resin composition, a method for producing a resin composition, a resin molded body, and a method for producing a resin molded body, all of which are capable of obtaining a resin composition having excellent light stability while maintaining the inherent transparency and heat resistance of methacrylic resins.
• “Monomer” means a compound that has a polymerizable carbon-carbon double bond.
• the term “repeating unit” refers to a unit derived from a monomer formed by polymerization of the monomer.
• the repeating unit may be a unit formed directly by a polymerization reaction, or may be a unit in which a part of the unit is converted into a different structure by treating the polymer.
• “(Meth)acrylate” means either or both of “acrylate” and “methacrylate”.
• “(Meth)acryloyl” means one or both of "acryloyl” and “methacryloyl”.
• (Meth)acrylic acid means either or both of “acrylic acid” and “methacrylic acid”.
• Conjugation refers to the overlap of p orbitals across an intervening ⁇ bond.
• Non-conjugated means that no conjugation occurs.
• the term “resin composition obtained” means a resin composition obtained by radical polymerization of a monomer mixture containing a monomer composition.
• the term “resin molded article obtained” refers to a resin molded article obtained by molding a resin composition.
• “% by mass” indicates the content of a given component in a total amount of 100% by mass.
• the “mass average molecular weight” is a value measured by gel permeation chromatography using standard polystyrene as a standard sample.
• UV and “ultraviolet” refer to light primarily having a wavelength range of 295-430 nm.
• Transition metal refers to a metallic element located in Groups 3 to 12 of the periodic table.
• the transition metals are scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), lanthanum (La), cerium (Ce), praseodymium (Pr), and arsenic (Ar).
• Nd neodymium
• Pm promethium
• Sm samarium
• Eu europium
• Gd gadolinium
• Tb terbium
• Dy dysprosium
• Ho holmium
• Er erbium
• Tm thulium
• Yb ytterbium
• Lu hafnium
• Group 13 element means an element located in Group 13 of the periodic table, typically boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl).
• Period Table means "Periodic Table of Elements”("Periodic Table of Elements", [online], National Center for Biotechnology Information, [searched November 7, 2022], Internet, ⁇ URL: https://pubchem.ncbi.nlm.nih.gov/periodic-table/>).
• a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower and upper limits, and "A ⁇ B" means greater than or equal to A and less than or equal to B.
• the monomer composition according to the first embodiment of the present invention comprises methyl methacrylate, an ⁇ -olefin, and methyl isobutyrate, the content of the methyl isobutyrate being more than 260 ppm by mass relative to the total mass of the monomer composition, and the ⁇ -olefin comprising at least one selected from the group consisting of 2-ethyl-1-hexene, 1-octene, and 1-dodecene (hereinafter, unless otherwise specified, " ⁇ -olefin” refers to at least one selected from the group consisting of 2-ethyl-1-hexene, 1-octene, and 1-dodecene).
• other components may be included within a range that does not impair the effects of the present invention.
• the monomer composition according to the present embodiment contains methyl methacrylate.
• Methyl methacrylate can be produced by, for example, the acetone cyanohydrin method, the new acetone cyanohydrin method, the C4 direct oxidation method, the direct methacrylate method, the ethylene method, the new ethylene method, or the like.
• Methyl methacrylate obtained by thermally decomposing a resin composition obtained by polymerizing a monomer composition containing methyl methacrylate may also be used. It is more preferable that the methyl methacrylate is methyl methacrylate obtained by thermally decomposing a resin composition obtained by polymerizing a monomer composition containing methyl methacrylate.
• the monomer composition according to the present embodiment contains methyl methacrylate, so that a resin composition that ensures excellent light stability and the inherent heat resistance of methacrylic resins can be provided.
• the lower limit of the content of methyl methacrylate relative to the total mass of the monomer composition is not particularly limited, but is preferably 85 mass% or more, more preferably 90 mass% or more, even more preferably 95 mass% or more, and particularly preferably 97 mass% or more.
• the upper limit of the content of methyl methacrylate is not particularly limited, but is usually 99.99 mass% or less, and may be 99.98 mass% or less or 99.97 mass% or less.
• the ranges include 85 mass% or more and 99.99 mass% or less, 90 mass% or more and 99.98 mass% or less, 95 mass% or more and 99.97 mass% or less, 97 mass% or more and 99.97 mass% or less, and 97 mass% or more and 99.97 mass% or less.
• the total content of methyl methacrylate, ⁇ -olefin, and methyl isobutyrate relative to the total mass of the monomer composition according to this embodiment is not particularly limited, and is usually 100 mass% or less.
• the monomer composition according to the present embodiment contains at least one ⁇ -olefin selected from the group consisting of 2-ethyl-1-hexene, 1-octene, and 1-dodecene, and thus can provide a resin composition having excellent light stability.
• the ⁇ -olefin may be used alone or in any combination of two or more kinds in any ratio.
• the lower limit of the ⁇ -olefin content relative to the total mass of the monomer composition according to this embodiment is not particularly limited, but since a resin composition with good light stability can be provided, it is preferably 0.1 ppm by mass or more, more preferably 10 ppm by mass or more, even more preferably 60 ppm by mass or more, even more preferably 80 ppm by mass or more, and particularly preferably 100 ppm by mass or more.
• the upper limit of the ⁇ -olefin content relative to the total mass of the monomer composition according to this embodiment is not particularly limited, but since a resin composition capable of maintaining good heat resistance can be provided, it is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, even more preferably 4,000 ppm by mass or less, even more preferably 3,000 ppm by mass or less, and particularly preferably 2,000 ppm by mass or less.
• the content of the ⁇ -olefin relative to the total mass of the monomer composition according to the present embodiment is preferably 0.1 mass ppm or more and 10,000 mass ppm or less, more preferably 10 mass ppm or more and 5,000 mass ppm or less, even more preferably 60 mass ppm or more and 4,000 mass ppm or less, even more preferably 80 mass ppm or more and 3,000 mass ppm or less, and particularly preferably 100 mass ppm or more and 2,000 mass ppm or less.
• the above content is the total content of the two or more kinds of ⁇ -olefins.
• the above-mentioned ⁇ -olefins are believed to have excellent radical scavenging properties because the coupling products between olefins to which radicals generated by ultraviolet light are added are stable.
• 2-ethyl-1-hexene, 1-octene, and 1-dodecene tend to remain in the resin composition obtained without volatilizing due to heating during polymerization. Therefore, they can fully contribute to improving the light stability of the resin composition obtained by polymerization of the monomer composition.
• At least one ⁇ -olefin selected from the group consisting of 2-ethyl-1-hexene, 1-octene, and 1-dodecene is likely to exhibit the effect of improving light stability even at a small content. As described below, the effect of improving light stability by ⁇ -olefins is thought to be related to hydrogen bonded to carbon adjacent to the double bond.
• the ⁇ -olefin among 2-ethyl-1-hexene, 1-octene, and 1-dodecene, one or more selected from 1-octene and 2-ethyl-1-hexene are more preferable, and 1-octene is even more preferable because it is likely to remain in the resin composition after polymerization.
• the proportion of 1-octene in the ⁇ -olefin is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, and is usually 100% by mass or less, relative to the total mass of the ⁇ -olefins.
• the content of at least one compound selected from the group consisting of transition metal compounds and Group 13 element compounds is preferably 0 ppm by mass or more and 2 ⁇ 10 4 ppm by mass or less, based on the total mass of the ⁇ -olefins.
• the ⁇ -olefin in this embodiment does not have a resonance stabilization effect and is significantly less reactive than methyl methacrylate, which is a conjugated monomer. Therefore, unless a specific polymerization catalyst such as at least one compound selected from the group consisting of transition metal compounds and Group 13 element compounds is used and a special condition is used in which the effect of the catalyst is exerted, unreacted ⁇ -olefin (hereinafter also referred to as " ⁇ -olefin monomer”) remains in the resulting resin composition. It is considered that the ⁇ -olefin monomer remaining in the resin composition can provide a resin composition with good light stability.
• a specific polymerization catalyst such as at least one compound selected from the group consisting of transition metal compounds and Group 13 element compounds
• the content of the at least one compound is preferably 2 x 10 4 mass ppm or less, more preferably 1 x 10 4 mass ppm or less, even more preferably 1,000 mass ppm or less, particularly preferably 500 mass ppm or less, and particularly preferably not contained.
• “not contained” means that it is below the detection limit.
• the at least one type of compound may be, for example, a compound of a transition metal of Groups 5 to 11 having a chelating ligand, or a Lewis acid catalyst.
• the transition metal include vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, platinum, ruthenium, cobalt, rhodium, nickel, palladium, and copper.
• the transition metal is preferably a transition metal of Groups 8 to 11, more preferably a transition metal of Group 10, and even more preferably nickel (Ni) or palladium (Pd). These transition metals may be used alone or in combination of two or more.
• the chelating ligand has at least two atoms selected from the group consisting of P, N, O, and S, includes bidentate or multidentate ligands, and is electronically neutral or anionic.
• Examples of chelating ligand structures are given in a review by Ittel et al. (Ittel et al., "Late-Metal Catalysts for Ethylene Homo- and Copolymerization", Chemical Reviews, March 25, 2000, Vol. 100, No. 4, pp. 1169-1204).
• Examples of the chelating ligand include bidentate anionic P, O ligands.
• Examples of the bidentate anionic P,O ligand include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate.
• Examples of the chelating ligand other than the bidentate anionic P,O ligand include bidentate anionic N,O ligand.
• Examples of the bidentate anionic N,O ligand include salicylaldiminate and pyridine carboxylic acid.
• Examples of the chelating ligand other than the bidentate anionic P,O ligand and the bidentate anionic N,O ligand include diimine ligand, diphenoxide ligand, and diamide ligand.
• typical examples of catalysts that are compounds of transition metals of Groups 5 to 11 having the chelating ligand include so-called SHOP catalysts and Drent catalysts.
• the SHOP catalysts are catalysts in which a phosphorus-based ligand having an aryl group that may have a substituent is coordinated to nickel metal.
• the Drent catalysts are catalysts in which a phosphorus-based ligand having an aryl group that may have a substituent is coordinated to palladium metal.
• Typical Lewis acid catalysts include cationic complexes of divalent palladium or platinum.
• the cationic complexes of divalent palladium or platinum exhibit Lewis acidity and are useful as Lewis acid catalysts for Diels-Alder reactions and the like.
• Compounds of the Group 13 elements boron and aluminum, the 4th period transition metal titanium, and the 5th period transition metal zirconium are also preferred because they exhibit Lewis acidity.
• Methyl isobutyrate is one of the components contained in the monomer composition according to the present embodiment.
• the content of the methyl isobutyrate relative to the total mass of the monomer composition is more than 260 ppm by mass, a resin composition having excellent light stability can be provided.
• the lower limit of the content of methyl isobutyrate relative to the total mass of the monomer composition according to this embodiment is usually more than 260 ppm by mass, preferably 270 ppm by mass or more, more preferably 280 ppm by mass or more, even more preferably 290 ppm by mass or more, still more preferably 450 ppm by mass or more, and particularly preferably 500 ppm by mass or more, since a resin composition having good light stability can be provided.
• the upper limit of the content of methyl isobutyrate relative to the total mass of the monomer composition according to this embodiment is not particularly limited, but since a resin composition capable of maintaining good heat resistance can be provided, it is preferably 20,000 ppm by mass or less, more preferably 15,000 ppm by mass or less, even more preferably 10,000 ppm by mass or less, even more preferably 5,000 ppm by mass or less, and particularly preferably 3,000 ppm by mass or less.
• the content of methyl isobutyrate relative to the total mass of the monomer composition according to this embodiment is preferably more than 260 ppm by mass and not more than 20,000 ppm by mass, more preferably from 270 ppm by mass to 20,000 ppm by mass, even more preferably from 280 ppm by mass to 15,000 ppm by mass, even more preferably from 290 ppm by mass to 10,000 ppm by mass, particularly preferably from 450 ppm by mass to 5,000 ppm by mass, and most preferably from 500 ppm by mass to 3,000 ppm by mass.
• the upper limit of the ratio of the ⁇ -olefin content to the methyl isobutyrate content is not particularly limited, but from the viewpoint of providing a resin molded product with good light stability due to the interaction between methyl isobutyrate and ⁇ -olefin, it is preferably 1,000 or less, more preferably 500 or less, even more preferably 300 or less, even more preferably 100 or less, particularly preferably 10 or less, and most preferably 5 or less.
• the lower limit of the ratio of [ ⁇ -olefin mass]/[methyl isobutyrate mass] is not particularly limited, but from the viewpoint of providing good heat resistance to the resin molded product, it is preferably 0.00001 or more, more preferably 0.0001 or more, even more preferably 0.001 or more, even more preferably 0.01 or more, particularly preferably 0.1 or more, and most preferably 0.2 or more.
• preferred ranges for the ratio of [mass of ⁇ -olefin]/[mass of methyl isobutyrate] include 0.00001 to 1,000, 0.0001 to 500, 0.001 to 300, 0.01 to 100, 0.1 to 10, and 0.2 to 5.
• the ratio of [mass of ⁇ -olefin]/[mass of methyl isobutyrate] is more preferably 0.0001 to 500, and even more preferably 0.001 to 300.
• the monomer composition according to the present embodiment may contain a monomer other than methyl methacrylate.
• “monomer” means an unpolymerized compound.
• Examples of the monomer other than methyl methacrylate include the monomers shown in (1) to (16) below.
• the monomers shown in (1) to (16) below can be used alone or in any ratio and combination of two or more kinds.
• Methacrylic acid ester For example, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, or benzyl methacrylate.
• Acrylic acid ester For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, or 2-ethylhexyl acrylate.
• Unsaturated carboxylic acid For example, acrylic acid, methacrylic acid, maleic acid, or itaconic acid.
• Unsaturated carboxylic acid anhydride For example, maleic anhydride, or itaconic anhydride.
• Maleimide For example, N-phenylmaleimide, or N-cyclohexylmaleimide.
• Hydroxy group-containing vinyl monomer For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, or 2-hydroxypropyl methacrylate.
• Vinyl esters For example, vinyl acetate, or vinyl benzoate.
• Nitrogen-containing vinyl monomers For example, methacrylamide, or acrylonitrile.
• Epoxy group-containing monomer For example, glycidyl acrylate, or glycidyl methacrylate.
• Aromatic vinyl monomers For example, styrene, or alpha-methylstyrene.
• Alkanediol di(meth)acrylate For example, ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, or 1,6-hexanediol di(meth)acrylate.
• Polyalkylene glycol di(meth)acrylate For example, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol (meth)acrylate, tetraethylene glycol di(meth)acrylate, or polyethylene glycol di(meth)acrylate.
• Vinyl monomers having two or more ethylenically unsaturated bonds in the molecule For example, divinylbenzene.
• Vinyl ester prepolymers obtained by modifying the terminals of epoxy groups with acrylics.
• the monomer is preferably at least one acrylic ester selected from the group consisting of methyl acrylate, ethyl acrylate, and n-butyl acrylate, and more preferably methyl acrylate or ethyl acrylate, in that it can provide a resin composition with an excellent balance of transparency, heat resistance, and moldability.
• the content of this acrylic ester is preferably 0% by mass or more and 30% by mass or less with respect to the total mass of the monomer composition.
• methyl methacrylate unit a repeating unit derived from methyl methacrylate
• styrene unit a repeating unit derived from styrene
• the content of styrene can be the content ratio of styrene units described in ⁇ 3-2.
• the monomer composition preferably further contains at least one compound selected from the group consisting of methyl propionate, methyl pyruvate, and methyl 2-methylbutyrate.
• the monomer composition according to this embodiment contains at least one compound selected from the group consisting of methyl propionate, methyl pyruvate, and methyl 2-methylbutyrate
• the total content of methyl isobutyrate, methyl propionate, methyl pyruvate, and methyl 2-methylbutyrate relative to the total mass of the monomer composition is within the range of the methyl isobutyrate content described above.
• the total content of methyl propionate, methyl pyruvate, and methyl 2-methylbutyrate relative to the total mass of the monomer composition is preferably 5 ppm by mass or more, more preferably 10 ppm by mass or more, even more preferably 15 ppm by mass or more, particularly preferably 20 ppm by mass or more, and most preferably 25 ppm by mass or more, and preferably 20,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, even more preferably 1,000 ppm by mass or less, particularly preferably 500 ppm by mass or less, and most preferably 100 ppm by mass or less. It is preferable that the amount is within the range of the methyl isobutyrate content described above.
• preferred ranges for the total content of methyl propionate, methyl pyruvate, and methyl 2-methylbutyrate relative to the total mass of the monomer composition according to this embodiment include ranges of 5 ppm by mass to 20,000 ppm by mass, 10 ppm by mass to 5,000 ppm by mass, 15 ppm by mass to 1,000 ppm by mass, 20 ppm by mass to 500 ppm by mass, and 25 ppm by mass to 100 ppm by mass.
• the monomer composition according to the present embodiment may contain other additives.
• the additives include known additives such as a mold release agent, a heat stabilizer, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer other than ⁇ -olefin and methyl isobutyrate, an ultraviolet absorber, a flame retardant, a flame retardant assistant, a filler, a pigment, a dye, a silane coupling agent, a leveling agent, an antifoaming agent, and a fluorescent agent.
• the additives may be used alone or in any combination of two or more kinds in any ratio.
• the ⁇ -olefin and methyl isobutyrate exhibit excellent light stability due to a mechanism of action different from that of commonly known UV absorbers and radical scavengers (HALS). Therefore, it is also possible to use the ⁇ -olefin and methyl isobutyrate in combination with additives such as UV absorbers and HALS.
• additives such as UV absorbers and HALS.
• the monomer composition according to this embodiment may also contain compounds that are inevitably mixed into methyl methacrylate, such as methacrolein and methanol.
• the polymerizable composition according to the second embodiment of the present invention is one aspect of a raw material for obtaining a resin composition according to the third embodiment of the present invention described later.
• the product also referred to as "polymerizable composition (X2)
• X2 polymerizable composition containing the monomer composition and, if necessary, a known radical polymerization initiator.
• radical polymerization initiator examples include known azo compounds such as 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile); known organic peroxides such as benzoyl peroxide and lauroyl peroxide; and the like. These can be used alone or in any combination of two or more kinds in any ratio. If necessary, known polymerization accelerators such as amines and mercaptans can be used in combination with the radical polymerization initiator.
• the content of the radical polymerization initiator in the polymerizable composition (X2) is not particularly limited, and can be appropriately determined by a person skilled in the art according to well-known techniques. Specifically, the content of the radical polymerization agent may be 0.005 parts by mass or more and 5 parts by mass or less, or 0.01 parts by mass or more and 1.0 parts by mass or less, relative to 100 parts by mass of the total mass of the polymerizable composition (X2).
• Additives> The mode of the additives is the same as that described in ⁇ 1-6. Additives>.
• the additive may be of one type or of two or more types.
• the resin composition according to the third embodiment of the present invention contains at least a methacrylic polymer (P), an ⁇ -olefin, and methyl isobutyrate.
• a resin composition comprising: a content of the methyl isobutyrate exceeding 49 ppm by mass based on a total mass of the resin composition; and the ⁇ -olefin is 2-ethyl-1-hexene, 1-octene, and
• the resin composition includes at least one member selected from the group consisting of 1-dodecene.
• the resin composition according to the present embodiment may be a composition containing a polymer of the monomer composition according to the first embodiment of the present invention
• the polymerizable monomer composition according to the second embodiment of the present invention may be a composition containing a polymer of the monomer composition according to the first embodiment of the present invention.
• the composition may be a composition obtained by radical polymerization.
• the resin composition according to this embodiment contains the methacrylic polymer (P), and thus can provide a resin molded article having excellent heat resistance and good transparency.
• the resin composition contains a methacrylic polymer (P), and by containing an ⁇ -olefin and a specific content of methyl isobutyrate, the ⁇ -olefin and methyl isobutyrate are present in the polymerization chain of the methacrylic polymer (P) in a monomeric state, and even if exposed to UV for a long period of time, the generation of a yellow tinge is suppressed, and further, a resin molded article in which a decrease in photostability is suppressed can be provided.
• the form of the resin composition is not particularly limited, but is usually a solid.
• the state of methyl isobutyrate is the same as that described in ⁇ 1-3. Methyl isobutyrate>.
• the state of ⁇ -olefin is the same as that described in ⁇ 1-2.
• the content of the methacrylic polymer (P) relative to the total mass of the resin composition is not particularly limited, but from the viewpoint of obtaining good heat resistance, it is usually 80.0 mass% or more, preferably 85.0 mass% or more, more preferably 90.0 mass% or more, even more preferably 95.0 mass% or more, and particularly preferably 99.0 mass% or more.
• this content is usually 99.99 mass% or less, preferably 99.9785 mass% or less, more preferably 99.97 mass% or less, even more preferably 99.95 mass% or less, and particularly preferably 99.90 mass% or less.
• the above upper and lower limits can be combined arbitrarily.
• preferred ranges of the content of the methacrylic polymer (P) include 80.0% by mass or more and 99.99% by mass or less, 85.0% by mass or more and 99.9785% by mass or less, 90.0% by mass or more and 99.97% by mass or less, 95.0% by mass or more and 99.95% by mass or less, and 99.0% by mass or more and 99.90% by mass or less.
• the above content is the total content of the two or more types of methacrylic polymers (P).
• the content of ⁇ -olefin relative to the total mass of the resin composition is not particularly limited. From the viewpoint of obtaining excellent light stability, the content of ⁇ -olefin is usually 0.1 ppm by mass or more, preferably 10 ppm by mass or more, more preferably 60 ppm by mass or more, even more preferably 80 ppm by mass or more, even more preferably 90 ppm by mass or more, and particularly preferably 100 ppm by mass or more.
• the upper limit of the ⁇ -olefin content relative to the total mass of the resin composition is not particularly limited, but from the viewpoint of improving the heat resistance of the resin molded body, it is usually 10,000 ppm by mass or less, preferably 5,000 ppm by mass or less, more preferably 4,000 ppm by mass or less, even more preferably 3,000 ppm by mass or less, even more preferably 2,000 ppm by mass or less, and particularly preferably 1,000 ppm by mass or less.
• preferred ⁇ -olefin contents include ranges of 0.1 ppm by mass to 10,000 ppm by mass, 10 ppm by mass to 5,000 ppm by mass, 60 ppm by mass to 4,000 ppm by mass, 80 ppm by mass to 3,000 ppm by mass, 90 ppm by mass to 2,000 ppm by mass, and 100 ppm by mass to 1,000 ppm by mass.
• the ⁇ -olefin content is more preferably 10 ppm by mass to 5,000 ppm by mass, and even more preferably 100 ppm by mass to 2,000 ppm by mass.
• the lower limit of the content of methyl isobutyrate relative to the total mass of the resin composition is usually more than 49 ppm by mass, preferably 50 ppm by mass or more, more preferably 60 ppm by mass or more, even more preferably 80 ppm by mass or more, particularly preferably 100 ppm by mass or more, and most preferably 200 ppm by mass or more, from the viewpoint of obtaining excellent light stability.
• the upper limit of the content of methyl isobutyrate relative to the total mass of the resin composition is not particularly limited, but from the viewpoint of improving the heat resistance of the resin molded body, it is preferably 20,000 ppm by mass or less, more preferably 15,000 ppm by mass or less, even more preferably 10,000 ppm by mass or less, particularly preferably 5,000 ppm by mass or less, and most preferably 3,000 ppm by mass or less.
• methyl isobutyrate content examples include more than 49 ppm by mass and not more than 20,000 ppm by mass, 50 ppm by mass or more and not more than 20,000 ppm by mass, 60 ppm by mass or more and not more than 15,000 ppm by mass, 80 ppm by mass or more and not more than 10,000 ppm by mass, 100 ppm by mass or more and not more than 5,000 ppm by mass, and 200 ppm by mass or more and not more than 3,000 ppm by mass.
• the content of methyl isobutyrate is more preferably 10 ppm by mass or more and not more than 20,000 ppm by mass, and even more preferably 30 ppm by mass or more and not more than 15,000 ppm by mass.
• the monomer composition according to the first embodiment of the present invention contains methyl methacrylate, an ⁇ -olefin, and a specific content of methyl isobutyrate.
• a resin composition obtained by radical polymerization of a polymerizable composition (X2) containing the monomer composition has excellent light stability and is inhibited from yellowing while ensuring excellent heat resistance.
• the reason why the monomer composition according to the first embodiment of the present invention contains an ⁇ -olefin and a specific content of methyl isobutyrate, and thereby a resin composition having excellent light stability and suppressed yellowing while ensuring excellent heat resistance can be obtained is presumed to be as follows.
• radical species usually cause the methacrylic resin to yellow and lose its mechanical strength due to a decrease in molecular weight.
• the ⁇ -olefin and a specific content of methyl isobutyrate contained in the monomer composition according to the first embodiment of the present invention do not provide a resonance stabilization effect and have significantly lower reactivity than the conjugated monomer methyl methacrylate. Therefore, unless special conditions are used, unreacted ⁇ -olefin (also called ⁇ -olefin monomer) and unreacted methyl isobutyrate (also called methyl isobutyrate monomer) remain in the resulting resin composition. It is believed that these unreacted ⁇ -olefins and methyl isobutyrate function as radical scavengers that capture the radical species. As a result, the hydrogen atom bonded to the carbon atom adjacent to the double bond site is extracted from the unreacted ⁇ -olefin, capturing the radical species.
• the upper limit of the ratio of the ⁇ -olefin content to the methyl isobutyrate content in the resin composition according to this embodiment (also referred to as the "ratio of [ ⁇ -olefin mass]/[methyl isobutyrate mass]”) is not particularly limited, but from the viewpoint of improving the light stability of the resin molded body due to the interaction between methyl isobutyrate and ⁇ -olefin, it is preferably 1,000 or less, more preferably 500 or less, even more preferably 300 or less, even more preferably 100 or less, particularly preferably 10 or less, and most preferably 5 or less.
• the lower limit of the ratio of [ ⁇ -olefin mass]/[methyl isobutyrate mass] is not particularly limited, but from the viewpoint of improving the heat resistance of the resin molded body, it is preferably 0.00001 or more, more preferably 0.0001 or more, even more preferably 0.001 or more, even more preferably 0.01 or more, particularly preferably 0.05 or more, and most particularly preferably 0.1 or more.
• preferred ranges for the ratio of [mass of ⁇ -olefin]/[mass of methyl isobutyrate] include 0.00001 to 1,000, 0.0001 to 500, 0.001 to 300, 0.01 to 100, 0.05 to 10, and 0.1 to 5.
• the ratio of [mass of ⁇ -olefin]/[mass of methyl isobutyrate] is more preferably 0.0001 to 500, and even more preferably 0.001 to 300.
• the methacrylic polymer (P) is one of the components contained in the resin composition according to this embodiment.
• the resin composition can improve transparency, and can suppress decomposition due to heat or light, thereby improving thermoformability, heat resistance, and mechanical strength.
• the resin composition has high light stability, and it is possible to obtain a methacrylic resin molded article that maintains its heat resistance.
• the content of methyl methacrylate units in the methacrylic polymer (P) is not particularly limited, but from the viewpoint of good heat resistance, it is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and is usually 100% by mass or less, based on the total mass of the methacrylic polymer (P).
• the methacrylic polymer (P) is preferably a copolymer methacrylic polymer (P1) containing methyl methacrylate units and, if necessary, repeating units derived from an acrylic ester (hereinafter also referred to as "acrylic ester units") or styrene units.
• the arrangement of these copolymers is not particularly limited, and may be, for example, a random copolymer, a block copolymer, or an alternating copolymer, but a random copolymer is preferred.
• the repeating unit derived from the acrylic acid ester is a repeating unit derived from an acrylic acid ester having an alkyl group having 1 to 6 carbon atoms in the side chain.
• the monomer constituting this unit is not particularly limited as long as it is a monomer that can be copolymerized with methyl methacrylate.
• acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, or tert-butyl acrylate can be mentioned. These may be used alone or in any ratio and combination of two or more.
• At least one acrylic acid ester selected from the group consisting of methyl acrylate, ethyl acrylate, and n-butyl acrylate, and more preferably methyl acrylate or ethyl acrylate.
• the content of methyl methacrylate units in the methacrylic polymer (P1) is not particularly limited, but from the viewpoint of good heat resistance, it is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and is usually 100% by mass or less, based on the total mass of the methacrylic polymer (P1).
• the content of the acrylic acid ester units in the methacrylic polymer (P1) is not particularly limited, but from the viewpoint of obtaining good heat resistance and light stability, it is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less, and is usually 0% by mass or more. Note that when the methacrylic polymer (P1) contains two or more types of acrylic acid ester units, the above content is the total content of the two or more types of acrylic acid ester units.
• the content of styrene units in the methacrylic polymer (P1) is not particularly limited, but from the viewpoint of good transparency, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less, and is usually 0% by mass or more.
• the methacrylic polymer (P) in this embodiment can contain a structural unit derived from a polyfunctional monomer containing two or more radically polymerizable functional groups in one molecule (hereinafter referred to as a "polyfunctional monomer unit"), within the range in which the effects of the invention can be obtained.
• the radical polymerizable functional group referred to here may be any group having a carbon-carbon double bond and capable of radical polymerization, and specific examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.
• a (meth)acryloyl group is preferred from the viewpoint of excellent storage stability of a compound having a radical polymerizable functional group and ease of controlling the polymerizability of the compound.
• the radical polymerizable functional groups in a monomer having two radical polymerizable functional groups may be the same or different.
• the methacrylic polymer (P) contains a polyfunctional monomer unit, the solvent resistance, chemical resistance, and the like can be improved.
• the polyfunctional monomer includes, but is not limited to, allyl methacrylate, allyl acrylate, ethylene glycol di(meth)acrylate, ethylene glycol tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. These may be used alone or in any combination of two or more in any ratio. Of these, from the viewpoint of better solvent resistance and chemical resistance, it is more preferable that the polyfunctional monomer is selected from ethylene glycol di(meth)acrylate and neopentyl glycol di(meth)acrylate, and even more preferable that it is ethylene glycol di(meth)acrylate.
• the mass average molecular weight (Mw) of the methacrylic polymer (P) measured by gel permeation chromatography (GPC) is not particularly limited.
• the mass average molecular weight (Mw) can be appropriately set depending on the intended use of the resin molded body. For example, it may be 10,000 or more, 100,000 or more, or 150,000 or more, or 1,000,000 or less, 2,000,000 or less, or 4,000,000 or less. By appropriately increasing the mass average molecular weight, it is possible to improve the solvent resistance and chemical resistance.
• the mass average molecular weight (Mw) of the methacrylic polymer (P) can be controlled by adjusting the polymerization temperature, polymerization time, amount of polymerization initiator added, or the type and amount of the series transfer agent added.
• the resin composition preferably further contains at least one compound selected from the group consisting of methyl propionate, methyl pyruvate, and methyl 2-methylbutyrate.
• the resin composition according to this embodiment contains at least one compound selected from the group consisting of methyl propionate, methyl pyruvate, and methyl 2-methylbutyrate
• the total content of methyl isobutyrate, methyl propionate, methyl pyruvate, and methyl 2-methylbutyrate relative to the total mass of the resin composition is an amount that falls within the range of the methyl isobutyrate content described above.
• the total content of methyl propionate, methyl pyruvate, and methyl 2-methylbutyrate relative to the total mass of the resin composition is preferably 5 ppm by mass or more, more preferably 10 ppm by mass or more, even more preferably 15 ppm by mass or more, particularly preferably 30 ppm by mass or more, and most preferably 60 ppm by mass or more, and also preferably 20,000 ppm by mass or less, more preferably 15,000 ppm by mass or less, even more preferably 10,000 ppm by mass or less, particularly preferably 5,000 ppm by mass or more, and most preferably 3,000 ppm by mass or more.
• preferred ranges for the total content of methyl propionate, methyl pyruvate, and methyl 2-methylbutyrate relative to the total mass of the resin composition according to this embodiment include ranges of 5 ppm by mass to 20,000 ppm by mass, 10 ppm by mass to 15,000 ppm by mass, 15 ppm by mass to 10,000 ppm by mass, 15 ppm by mass to 10,000 ppm by mass, 30 ppm by mass to 5,000 ppm by mass, and 60 ppm by mass to 3,000 ppm by mass.
• the resin composition according to this embodiment contains the methacrylic polymer (P), an ⁇ -olefin, and a specific amount of methyl isobutyrate, and therefore has excellent light stability.
• the yellowness index (YI) of the test piece measured in accordance with ASTM D1925 between before the start of the UV exposure test and 200 hours after the start of the UV exposure test is 6.0 or less, preferably 5.5 or less, more preferably 5.0 or less, even more preferably 4.5 or less, and particularly preferably 4.0 or less.
• the resin molded body according to the fourth embodiment of the present invention is a resin molded body containing the resin composition according to the third embodiment of the present invention. That is, the resin molded body according to this embodiment contains the resin composition according to the third embodiment of the present invention.
• a resin molded body having excellent light stability while maintaining the transparency and heat resistance inherent to methacrylic resin can be obtained.
• molding methods in the molding process include press molding, injection molding, gas-assisted injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, melt spinning, and the like.
• the resin molded body is not particularly limited as long as it is a molded body containing the above-mentioned resin composition, and a molded body consisting of only the resin composition substantially corresponds to both the resin composition and the resin molded body.
• the shape of the resin molded body is not limited to the following, but examples include granular pellets, plate-shaped resin molded bodies (resin plates), and sheet- or film-shaped resin molded bodies (resin sheets).
• the thickness of the resin molded body can be adjusted to any thickness as needed, from a thick plate to a thin film.
• the thickness can be 0.1 ⁇ m to 30 mm, or 1 mm to 30 mm.
• the resin molded article has excellent light stability because it contains the above-mentioned resin composition. That is, the resin molded product exhibits excellent light stability such that the yellowness index (YI), measured in accordance with ASTM D1925 during the period from before the start of the above-mentioned UV exposure test to 200 hours after the start of the UV exposure test, is 6.0 or less, preferably 5.5 or less, more preferably 5.0 or less, even more preferably 4.5 or less, and particularly preferably 4.0 or less.
• YI yellowness index
• the method for producing the resin composition or the resin molded article containing the resin composition (hereinafter, the resin composition and the resin molded article are collectively referred to as "resin composition, etc.") is not particularly limited.
• a specific method for producing the resin composition, etc. is, for example, a method including a radical polymerization step of radically polymerizing the polymerizable composition (X2) according to the second embodiment of the present invention, preferably the polymerizable composition (X2) containing the monomer composition according to the first embodiment of the present invention.
• the radical polymerization step may include a syrup preparation step of polymerizing a part of the polymerizable composition (X2) to prepare a syrup, and a polymerization step of polymerizing the polymerizable component in the syrup.
• "polymerizing a part of the polymerizable composition (X2)" in the syrup preparation step means polymerization so that the content of the methacrylic polymer in the obtained syrup is 10% by mass or more and 80% by mass or less, preferably 10% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less.
• the polymerization temperature when polymerizing the polymerizable composition (X2) is not particularly limited, and can be appropriately determined by a person skilled in the art according to well-known techniques. Usually, the temperature is appropriately set in the range of preferably 40°C or higher and 180°C or lower, more preferably 50°C or higher and 150°C or lower, depending on the type of radical polymerization initiator used.
• the polymerizable composition (X2) can be polymerized under multi-stage temperature conditions as necessary.
• the polymerization time can be appropriately determined depending on the progress of polymerization curing.
• Examples of the polymerization method for the polymerizable composition (X2) include bulk polymerization, suspension polymerization, emulsion polymerization, and dispersion polymerization, among which bulk polymerization is preferred from the viewpoint of productivity.
• Specific examples of methods for producing resin compositions include a method of obtaining a resin composition by bulk polymerization using a known cast polymerization method such as a cell cast method or a continuous cast method, or a method of obtaining a resin composition by molding a composition produced by a bulk polymerization method. It is more preferable to employ a method that utilizes cast polymerization (casting polymerization) from the viewpoint of further improving the heat resistance of the resin composition by increasing the molecular weight or introducing a crosslinked structure.
• the cast polymerization method for example, when obtaining a resin composition having a plate-like form, a cell cast method is used in which the space formed by two opposing glass plates or metal plates (SUS plates) and a gasket such as a soft resin tube arranged on the edge of the two plates is used as a mold, the polymerizable composition (X2) or a syrup obtained by polymerizing a part of the polymerizable composition (X2) is injected into the mold, the polymerization is completed by heat polymerization treatment, and the resin composition is taken out from the mold.
• SUS plates glass plates or metal plates
• a gasket such as a soft resin tube arranged on the edge of the two plates
• a continuous cast method in which the space formed by two stainless steel endless belts running in the same direction at the same speed and facing each other at a predetermined interval and a gasket such as a soft resin tube arranged on both sides of the belt is used as a mold, the polymerizable composition (X2) or a syrup obtained by polymerizing a part of the polymerizable composition (X2) is continuously injected into the mold from one end of the endless belt, the polymerization is completed by heat polymerization treatment, and the resin composition is continuously taken out from the other end of the endless belt.
• the spacing of the gaps in the mold can be appropriately adjusted by adjusting the thickness (diameter) of the gasket to obtain a resin composition of a desired thickness.
• the thickness of the plate-like resin composition is usually set in the range of 1 mm or more and 30 mm or less.
• resin composition and resin molded product
• resin composition are not particularly limited, and include vehicle components, medical components, toys, liquid containers, optical materials, signs, displays, decorative components, and building components.
• the present invention is preferably used as a light-transmitting member, particularly a transparent member, for use in either the face plate of an electronic device or the like.
• Methyl methacrylate Methyl methacrylate (manufactured by Mitsubishi Chemical Corporation) - Methyl isobutyrate (Tokyo Chemical Industry Co., Ltd.) ⁇ 1-Octene (Tokyo Chemical Industry Co., Ltd.) 2-Ethyl-1-hexene (Tokyo Chemical Industry Co., Ltd.)
• methyl methacrylate manufactured by Mitsubishi Chemical Corporation
• ICP emission spectrometer PerkinElmer, model name: Optima 8300
• Output 1,300 W
• Pump speed 1.0 mL/min
• Plasma gas flow rate 10 L/min
• Auxiliary gas flow rate 0.2 L/min
• Nebulizer gas flow rate 0.55 L/min
• Detector SCD (Segmented Array CCD) Integration time: Auto (1 to 5 sec)
• test solutions with different concentrations were prepared by diluting the target standard reagent with acetone, and a three-point calibration curve was created by gas chromatography mass spectrometry (GC/MS) measurement described later, and the content of each target substance in the sample was quantified.
• GC/MS gas chromatography mass spectrometry
• HDT deflection temperature under load
• the light stability test was carried out using a metal weather ultra-accelerated light stability tester (manufactured by Daipla Wintes Co., Ltd., model: DW-R8PL-A) equipped with a metal halide lamp (manufactured by Daipla Wintes Co., Ltd., model: MW-60W) and a light cut filter (manufactured by Daipla Wintes Co., Ltd., model: KF-1). Specifically, a test piece (50 mm long x 50 mm wide square, 3 mm thick) made of a resin composition was placed in the evaluation chamber of the metal weather ultra-accelerated light stability tester, and the test piece was irradiated with light from a metal halide lamp for 300 hours.
• a metal weather ultra-accelerated light stability tester manufactured by Daipla Wintes Co., Ltd., model: DW-R8PL-A
• a metal halide lamp manufactured by Daipla Wintes Co., Ltd., model: MW-60W
• a light cut filter manufactured
• the UV irradiation intensity was corrected so that the irradiation intensity at a wavelength of 300 to 400 nm measured with an ultraviolet illuminometer (manufactured by Ushio Denki Co., Ltd., model: UVP-365-03) was 130 mW/cm 2.
• the test piece was irradiated with visible light and UV from a metal halide lamp.
• the evaluation room of the Metal Weather ultra-accelerated light stability tester was set to an environment of 63° C. temperature and 50 RH %.
• Example 1 Production of syrup ⁇ -olefin 1-octene and methyl isobutyrate were added to a reactor (polymerization kettle) equipped with a cooling tube, a thermometer, and a stirrer, and methyl methacrylate was further fed. After bubbling with nitrogen gas while stirring, heating was started. When the internal temperature of the reactor reached 80°C, 0.12 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator and 0.075 parts of 1-dodecanethiol as a chain transfer agent were added, and the internal temperature of the reactor was further heated to 100°C and then maintained for 9 minutes.
• a reactor polymerization kettle equipped with a cooling tube, a thermometer, and a stirrer, and methyl methacrylate was further fed. After bubbling with nitrogen gas while stirring, heating was started. When the internal temperature of the reactor reached 80°C, 0.12 parts of 2,2'-azobis(2,4-dimethylvaleron
• the internal temperature of the reactor was cooled to room temperature, and a syrup containing 500 ppm each of 1-octene and methyl isobutyrate was obtained.
• the content of the polymer in the syrup was 25% by mass with respect to the total mass of the syrup.
• Examples 2 to 7, Reference Examples 1 to 6 A resin composition and a resin molded article were produced in the same manner as in Example 1, except that the composition of the monomer composition was changed as shown in Table 1. The composition of the obtained resin composition is shown in Table 1. The evaluation results of the properties of the obtained resin molded article are shown in Table 1.
• Examples 1 to 7 a monomer composition containing methyl methacrylate, an ⁇ -olefin, and methyl isobutyrate was used, in which the content of methyl isobutyrate relative to the total mass of the monomer composition was more than 260 ppm by mass, and the ⁇ -olefin contained at least one selected from the group consisting of 2-ethyl-1-hexene, 1-octene, and 1-dodecene.
• the resin compositions obtained by polymerizing these monomer compositions were resin compositions containing a methacrylic polymer (P), an ⁇ -olefin, and methyl isobutyrate, in which the content of methyl isobutyrate relative to the total mass of the resin composition was more than 49 ppm by mass, and the ⁇ -olefin contained at least one selected from the group consisting of 2-ethyl-1-hexene, 1-octene, and 1-dodecene. From Table 1, it can be seen that the resin molded bodies obtained by molding these resin compositions have excellent light stability while maintaining the transparency and heat resistance inherent to methacrylic resins.
• P methacrylic polymer
• ⁇ -olefin methyl isobutyrate
• the monomer compositions of Reference Examples 1, 2, 4, and 5 contain ⁇ -olefins, but the methyl isobutyrate content is 260 ppm by mass or less.
• the monomer composition of Reference Example 3 does not contain ⁇ -olefins, and the methyl isobutyrate content is 260 ppm by mass or less.
• the monomer composition of Reference Example 6 contains more than 260 ppm by mass of methyl isobutyrate, but does not contain ⁇ -olefins.
• the resin compositions of Reference Examples 1, 2, 4, and 5 contain ⁇ -olefins, but the methyl isobutyrate content is 49 ppm by mass or less.
• the monomer composition of Reference Example 3 does not contain ⁇ -olefins, and the methyl isobutyrate content is 49 ppm by mass or less.
• the monomer composition of Reference Example 6 contains more than 49 ppm by mass of methyl isobutyrate, but does not contain ⁇ -olefins.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=91084558

Family Applications (2)

Family Applications After (1)

Country Status (7)

Citations (6)

Family Cites Families (5)

• 2023
  • 2023-11-17 EP EP23891675.3A patent/EP4620985A1/en active Pending
  • 2023-11-17 JP JP2024558954A patent/JPWO2024106530A1/ja active Pending
  • 2023-11-17 WO PCT/JP2023/041408 patent/WO2024106530A1/ja not_active Ceased
  • 2023-11-17 WO PCT/JP2023/041381 patent/WO2024106522A1/ja not_active Ceased
  • 2023-11-17 TW TW112144417A patent/TWI900931B/zh active
  • 2023-11-17 CN CN202380079176.8A patent/CN120187769A/zh active Pending
  • 2023-11-17 TW TW112144416A patent/TWI900930B/zh active
  • 2023-11-17 KR KR1020257016324A patent/KR20250087716A/ko active Pending
  • 2023-11-17 KR KR1020257016323A patent/KR20250086783A/ko active Pending
  • 2023-11-17 CN CN202380079174.9A patent/CN120187766A/zh active Pending
  • 2023-11-17 JP JP2024558947A patent/JPWO2024106522A1/ja active Pending
  • 2023-11-17 EP EP23891667.0A patent/EP4620984A1/en active Pending
• 2025
  • 2025-05-14 US US19/207,763 patent/US20250270353A1/en active Pending
  • 2025-05-14 US US19/207,694 patent/US20250270358A1/en active Pending

Patent Citations (6)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events