Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • 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
  • 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
  • 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
  • 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
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • 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
• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/14—Organic medium
• • 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

Definitions

• the present invention relates to a monomer composition, a methacrylic resin composition and a resin molding.
• This application claims priority based on Japanese Patent Application No. 2021-085291 filed in Japan on May 20, 2021, the content of which is incorporated herein.
• Methacrylic resins are excellent in transparency, heat resistance, and weather resistance, and have well-balanced performance in resin physical properties such as mechanical strength, thermal properties, and moldability.
• methacrylic resin plates made of plate-shaped methacrylic resins are used for tanning beds, lighting equipment, skin therapy equipment, medical equipment, UV irradiation devices, equipment for growing animals and plants, skylights, HID lamps, and the like. It is used for translucent members.
• the methacrylic resin plate when the methacrylic resin plate is installed in an environment where it is exposed to UV such as direct sunlight or a UV lamp, the methacrylic resin plate has a yellowish color (yellowish, yellowish). was there. Therefore, there has been a demand for a methacrylic resin that does not develop a yellowish color even when exposed to UV for a long period of time, that is, a methacrylic resin that has excellent photostability.
• Patent Document 1 discloses that a monomer such as methyl methacrylate is polymerized in the presence of a hindered amine compound (HALS) having a specific structure, which is one of the photostabilizers.
• HALS hindered amine compound
• the present invention provides a methacrylic resin composition that has excellent light stability and suppressed yellowing while ensuring the excellent heat resistance of methacrylic resins;
• An object of the present invention is to provide a resin molded product; and a monomer composition for obtaining the methacrylic resin composition.
• the present invention has the following features. That is, the gist of the present invention is as follows.
• a monomer composition comprising methyl methacrylate and methyl isobutyrate, A monomer composition having a methyl isobutyrate content of more than 300 ppm by mass and not more than 50,000 ppm by mass relative to the total mass of the monomer composition.
• a monomer composition comprising methyl methacrylate and methyl isobutyrate, A monomer composition, wherein the content of methyl isobutyrate is 400 ppm by mass or more relative to the total mass of the monomer composition.
• a monomer composition comprising methyl methacrylate and methyl isobutyrate, A monomer composition, wherein the content of methyl isobutyrate is 500 ppm by mass or more relative to the total mass of the monomer composition.
• a methacrylic resin composition containing a methacrylic polymer (P) and methyl isobutyrate A methacrylic resin composition having a methyl isobutyrate content of 300 ppm by mass or more relative to the total mass of the methacrylic resin composition.
• a methacrylic resin composition containing a methacrylic polymer (P) and methyl isobutyrate A methacrylic resin composition having a methyl isobutyrate content of 500 ppm by mass or more relative to the total mass of the methacrylic resin composition.
• a methacrylic resin composition having excellent light stability and suppressed yellowing while ensuring the excellent heat resistance of the methacrylic resin; a resin molded article containing the methacrylic resin composition; and a monomer composition for obtaining the methacrylic resin composition;
• (meth)acrylate means at least one selected from “acrylate” and “methacrylate”
• “(meth)acrylic” is selected from “methacrylic” and “acrylic”.
• the "methacrylic polymer” may contain repeating units derived from acrylic monomers in addition to repeating units derived from methacrylic monomers.
• “monomer” means an unpolymerized compound
• “repeating unit” means a unit derived from the monomer formed by polymerizing the monomer.
• the repeating unit may be a unit directly formed by a polymerization reaction, or may be a unit in which some of the units are converted to another structure by treating the polymer.
• “% by mass” indicates the content of a specific component contained in 100% by mass of the total amount.
• UV means light mainly including light in a wavelength range of 295 nm or more and 430 nm or less, that is, light in a wavelength range of 380 nm or less.
• a monomer composition according to a first embodiment of the present invention comprises methyl methacrylate and methyl isobutyrate. Further, other components may be contained within a range that does not impair the effects of the present invention.
• Methyl methacrylate Since the monomer composition according to the present embodiment contains methyl methacrylate, it is possible to provide a methacrylic resin composition having good photostability and suppressed yellowing.
• the lower limit of the content of methyl methacrylate with respect to the total mass of the monomer composition according to the present embodiment is not particularly limited, but is preferably 85% by mass or more, more preferably 90% by mass or more, It is more preferably 95% by mass or more, and particularly preferably 97% by mass or more.
• the upper limit of the content of methyl methacrylate is usually less than 99.97% by mass, and may be 99.96% by mass or less or 99.95% by mass or less.
• the content of methyl methacrylate is, for example, 85% by mass or more and less than 99.97% by mass, 90% by mass or more and less than 99.97% by mass, 95% by mass or more and 99.96% by mass or less, and 97% by mass or more.
• a range of 99.95% by mass or less can be mentioned.
• the total content of methyl methacrylate and methyl isobutyrate with respect to the total mass of the monomer composition according to the present embodiment is not particularly limited, and is usually 100% by mass or less.
• Methyl isobutyrate Since the monomer composition according to the present embodiment contains methyl isobutyrate, it is possible to provide a methacrylic resin composition having good photostability and suppressed yellowing.
• the lower limit of the content of methyl isobutyrate with respect to the total mass of the monomer composition according to the present embodiment is usually more than 300 ppm by mass (that is, excluding the range of 300 mass ppm or less), preferably 400 mass ppm or more, more preferably 450 mass ppm or more, still more preferably 470 mass ppm or more, and particularly preferably 500 mass ppm or more.
• the upper limit of the content of methyl isobutyrate with respect to the total mass of the monomer composition according to the present embodiment is not particularly limited, but when the monomer composition is converted to a methacrylic resin composition, It is usually 50,000 mass ppm or less, preferably 25,000 mass ppm or less, more preferably 20,000 mass ppm or less, and 15,000 mass ppm or less, so that the heat resistance is not impaired. More preferably, it is particularly preferably 10,000 ppm by mass or less.
• the content of methyl isobutyrate with respect to the total mass of the monomer composition according to the present embodiment is preferably more than 300 mass ppm and 50,000 mass ppm or less, and more than 400 mass ppm and 25,000 mass ppm. It is more preferably no more than mass ppm, more preferably 450 mass ppm or more and 20,000 mass ppm or less, particularly preferably 470 mass ppm or more and 15,000 mass ppm or less, 500 mass ppm or more 10, It is most preferably 000 mass ppm or less.
• the monomer composition according to the present embodiment may contain methyl methacrylate and monomers other than methyl methacrylate.
• monomers other than methyl methacrylate include the following monomers 1) to 16).
• the following monomers 1) to 16) can be used singly or in combination of two or more at any ratio.
• 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 ester For example vinyl acetate or vinyl benzoate.
• Nitrogen-containing vinyl monomer For example, methacrylamide, or acrylonitrile.
• Epoxy group-containing monomer For example, glycidyl acrylate or glycidyl methacrylate.
• Aromatic vinyl monomer For example, styrene or ⁇ -methylstyrene.
• Alkanediol di(meth)acrylates For example, ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate or 1,6-hexanediol di(meth)acrylate.
• Polyoxyalkylene 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, polyethylene glycol di(meth)acrylate, or neopentyl glycol di(meth) ) acrylates.
• Vinyl monomer having two or more ethylenically unsaturated bonds in the molecule For example, divinylbenzene.
• the monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, and n-butyl acrylate from the viewpoint of excellent balance of transparency, heat resistance, and moldability of the methacrylic resin composition.
• the content of the acrylic acid ester is preferably 0% by mass or more and 30% by mass or less with respect to the total mass of the monomer composition.
• the monomer composition according to this embodiment may further contain at least one compound selected from the group consisting of methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate. It preferably further contains at least one compound selected from methyl and methyl 2-methylbutyrate.
• the lower limit of the total content of methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate with respect to the total mass of the monomer composition according to the present embodiment provides a methacrylic resin composition with better photostability. 20 mass ppm or more is preferable, 100 mass ppm or more is more preferable, 300 mass ppm or more is still more preferable, and 1,000 mass ppm or more is particularly preferable.
• the upper limit of the total content of methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate with respect to the total mass of the monomer composition according to the present embodiment is not particularly limited, but the monomer composition is a methacrylic resin. In terms of not impairing the heat resistance of the methacrylic resin when converted to a composition, it is usually 50,000 mass ppm or less, preferably 25,000 mass ppm or less, and 10,000 mass ppm or less. It is more preferably 7,000 mass ppm or less, and particularly preferably 5,000 mass ppm or less.
• the total content of methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate is 20 mass ppm or more and 50,000 mass ppm or less, 100 mass ppm or more and 25,000 mass ppm or less, and 300 mass ppm. ppm or more and 10,000 mass ppm or less, 300 mass ppm or more and 7,000 mass ppm or less, and 1,000 mass ppm or more and 5,000 mass ppm or less.
• the total content of methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate is more preferably 100 mass ppm or more and 25,000 mass ppm or less, and more preferably 300 mass ppm or more and 7,000 mass ppm. More preferably:
• methyl isobutyrate with respect to the total mass of the monomer composition methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate is preferably within the range of the content of methyl isobutyrate described above.
• methyl isobutyrate is believed to exhibit excellent photostability 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 methyl isobutyrate in combination with additives such as UV absorbers and HALS. By including methyl isobutyrate and the additive in the monomer composition, it is possible to provide a methacrylic resin composition and a resin molding with increased photostability at a lower cost.
• additives examples include release agents, lubricants, plasticizers, antioxidants, antistatic agents, light stabilizers other than methyl isobutyrate, ultraviolet absorbers, flame retardants, flame retardant aids, polymerization inhibitors, and fillers. , pigments, dyes, silane coupling agents, leveling agents, antifoaming agents, and fluorescent agents.
• release agents include release agents, lubricants, plasticizers, antioxidants, antistatic agents, light stabilizers other than methyl isobutyrate, ultraviolet absorbers, flame retardants, flame retardant aids, polymerization inhibitors, and fillers.
• pigments, dyes, silane coupling agents, leveling agents, antifoaming agents, and fluorescent agents can be used individually by 1 type or in combination of arbitrary 2 or more types.
• the monomer composition according to the present embodiment may contain compounds such as methacrolein and methanol that are unavoidably mixed with methyl methacrylate.
• the polymerizable composition (X2) according to the second embodiment of the present invention is one aspect of raw materials for obtaining the methacrylic resin composition according to the third embodiment of the present invention, which will be described later.
• the polymerizable composition (X2) according to the present embodiment is, for example, a polymerizable composition (X2-1) containing a raw material composition (X1) described later, methyl isobutyrate, and a known radical polymerization initiator; or Polymerizable composition (X2-2) containing the monomer composition according to the first embodiment of the present invention and a known radical polymerization initiator;
• the raw material composition (X1) is a component of the polymerizable composition (X2-1), and is the methacrylic polymer (P) contained in the methacrylic resin composition according to the third embodiment of the present invention. It is also a raw material component.
• the methacrylic polymer (P) includes repeating units derived from methyl methacrylate (hereinafter also referred to as "MMA") (hereinafter also referred to as "MMA units”) and repeating units derived from acrylic acid esters.
• the raw material composition (X1) used for the production of the methacrylic polymer (P1) containing the unit (hereinafter also referred to as "acrylic acid ester unit") is mainly described, but the acrylic acid ester is changed to styrene. Therefore, it can also be applied to the production of a methacrylic polymer (P2) containing MMA units and styrene-derived repeating units (hereinafter also referred to as "styrene units"). At this time, the content of styrene is ⁇ 3-1. Methacrylic polymer (P)> can be applied to the styrene unit content.
• Examples of the raw material composition (X1) include a composition containing only MMA and a composition containing the MMA and an acrylic acid ester. ⁇ 1-3. other monomers> or ⁇ 3-1. Methacrylic Polymer (P)> can be used the same monomer as the acrylic acid ester described.
• the raw material composition (X1) contains MMA and an acrylic ester, the photostability of the methacrylic resin composition is improved, and the resin molding containing the methacrylic resin composition is exposed to UV for a long time. It is possible to suppress the occurrence of yellowish color and deterioration of photostability.
• the content of MMA in the raw material composition (X1) is not particularly limited, and can improve the photostability of the methacrylic resin composition.
• a ratio similar to the content ratio of MMA units in the methacrylic polymer (P1) or the methacrylic polymer (P2) described in Methacrylic Polymer (P)> can be suitably applied.
• ⁇ 3-1 "With respect to the total mass of the methacrylic polymer (P1)” and “with respect to the total mass of the methacrylic polymer (P2)" in the methacrylic polymer (P)>, "raw material composition (X1) shall be read as "for the total mass of
• the content of the acrylic acid ester (M2) in the raw material composition (X1) is not particularly limited, and the light stability of the methacrylic resin composition can be improved, so ⁇ 3-1.
• a ratio similar to the content ratio of the acrylic acid ester unit contained in the methacrylic polymer (P1) or the methacrylic polymer (P2) described in Methacrylic Polymer (P)> can be suitably applied.
• ⁇ 3-1 A ratio similar to the content ratio of the acrylic acid ester unit contained in the methacrylic polymer (P1) or the methacrylic polymer (P2) described in Methacrylic Polymer (P)> can be suitably applied.
• ⁇ 3-1 is ⁇ 3-1.
• raw material composition (X1) shall be read as "for the total mass of From the viewpoint of excellent photostability of the methacrylic resin composition, ⁇ 1-3. other monomers> or ⁇ 3-1.
• Methacrylic Polymer (P)> can be applied to the same compound as the acrylic acid ester described in the section.
• the raw material composition (X1) may previously contain a polymer containing MMA units.
• the raw material composition (X1) can contain in advance the polymer (a) described later.
• the polymerizable composition (X2-1) becomes a viscous liquid (referred to as “syrup”), so that the polymerization time can be shortened and productivity can be improved. can be improved.
• a method for obtaining the above-mentioned syrup for example, a method of dissolving a polymer in the raw material composition (X1), or a known radical polymerization initiator is added to the raw material composition (X1), and a part thereof is polymerized. methods and the like.
• the polymerizable composition (X2-1) when the polymerizable composition (X2-1) is a syrup, it includes a composition containing the following polymer (a) and monomer composition (m).
• Monomer composition (m) a monomer composition containing 70.0% by mass or more of MMA and 30.0% by mass or less of an acrylic ester, or MMA50, based on the total mass of the monomer composition (m) A monomer composition containing 0% by mass or more and 50.0% by mass or less of styrene, or a monomer composition comprising 100% by mass of MMA.
• the content (unit: mass %) of the raw material composition (X1) contained in the polymerizable composition (X2-1) is not particularly limited, and the total amount of the polymerizable composition (X2-1) It can be in the range of 97.5% by mass or more and 99.99% by mass or less with respect to the mass.
• the monomer composition which is a component of the polymerizable composition (X2-2), is the monomer composition according to the first embodiment of the present invention, and according to the third embodiment of the present invention. It is a composition containing the raw material component of the methacrylic polymer (P) contained in the methacrylic resin composition.
• the content of the monomer composition according to the first embodiment of the present invention is 60% by mass or more and less than 100% by mass with respect to the total mass of the polymerizable composition (X2-2).
• the polymerizable composition (X2-2) contains other monomers copolymerizable with the monomers in the monomer composition (also simply referred to as "other monomers"). You can When the polymerizable composition (X2-2) contains another monomer, the content of the other monomer is 0% by mass with respect to the total mass of the polymerizable composition (X2-2) It is more than 40% by mass and less than 40% by mass.
• Other monomers> include the monomers 1) to 16) listed above.
• the above monomers 1) to 16) can be used singly or in combination of two or more at any ratio.
• a monomer selected from ethylene glycol dimethacrylate and neopentyl glycol dimethacrylate from the viewpoint of providing a methacrylic resin composition having an excellent balance between heat resistance and transparency. is preferred.
• radical polymerization initiators include known azo compounds such as 2,2′-azobis(isobutyronitrile) and 2,2′-azobis(2,4-dimethylvaleronitrile); benzoyl peroxide and lauroyl peroxide; well-known organic peroxides such as oxide; These can be used alone or in combination of two or more in any ratio.
• known polymerization accelerators such as amines and mercaptans can be used together 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 those 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 with respect to 100 parts by mass of the total mass of the polymerizable composition (X2), and 0.01 mass parts parts or more and 1.0 parts by mass or less.
• the polymerizable composition (X2) optionally contains a release agent, a heat stabilizer, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer other than methyl isobutyrate, an ultraviolet absorber, Contains additives selected from flame retardants, flame retardant aids, polymerization inhibitors, fillers, pigments, dyes, silane coupling agents, leveling agents, defoaming agents, fluorescent agents, chain transfer agents, etc. good too.
• the methacrylic resin composition according to the third embodiment of the present invention (hereinafter also simply referred to as "methacrylic resin composition”) comprises a methacrylic polymer (P) and a predetermined amount of methyl isobutyrate at least It is a methacrylic resin composition containing.
• the methacrylic resin composition according to this embodiment may be a composition obtained by radically polymerizing the polymerizable composition (X2) according to the second embodiment of the invention. Since the methacrylic resin composition according to the present embodiment contains the methacrylic polymer (P), it is possible to provide a resin molding having good transparency.
• the methacrylic resin composition suppresses yellowing even when exposed to UV for a long period of time, and further provides a resin molded article in which a decrease in photostability is suppressed. be able to.
• the form of the methacrylic resin composition is not particularly limited, it is usually solid.
• the content of the methacrylic polymer (P) with respect to the total mass of the methacrylic resin composition is not particularly limited, but from the viewpoint of good heat resistance, it is usually 95% by mass or more, and 97.5% by mass. It is preferably at least 98% by mass, more preferably at least 99.0% by mass. On the other hand, from the viewpoint of obtaining excellent photostability, this content is usually 99.99% by mass or less, preferably 99.9785% by mass or less, more preferably 99.97% by mass or less. It is preferably 99.95% by mass or less, more preferably 99.90% by mass or less, and particularly preferably 99.90% by mass or less.
• the above upper limit and lower limit can be combined arbitrarily.
• the preferred content of the methacrylic polymer (P) is 95% by mass or more and 99.99% by mass or less, 95% by mass or more and 99.9785% by mass or less, 97.5% by mass or more and 99.97% by mass or less. , 98 mass % or more and 99.95 mass % or less, and 99.0 mass % or more and 99.90 mass % or less.
• the methacrylic resin composition contains two or more methacrylic polymers (P)
• the above content is the total content of the two or more methacrylic polymers (P).
• the content of methyl isobutyrate relative to the total mass of the methacrylic resin composition is not particularly limited. From the viewpoint of obtaining excellent photostability, the content of methyl isobutyrate is usually 100 mass ppm or more, preferably 215 mass ppm or more, and 300 mass ppm or more, relative to the total mass of the methacrylic resin composition. It is more preferably at least 500 ppm by mass, particularly preferably at least 1,000 ppm by mass.
• the upper limit of the content of methyl isobutyrate contained in the methacrylic resin composition according to the present embodiment is not particularly limited, but from the viewpoint of improving the heat resistance of the resin molded product, it is usually 50,000 mass ppm or less. , preferably 25,000 mass ppm or less, more preferably 20,000 mass ppm or less, even more preferably 15,000 mass ppm or less, particularly 10,000 mass ppm or less preferable.
• the above upper limit and lower limit can be combined arbitrarily.
• the preferable content of methyl isobutyrate is 100 mass ppm or more and 50,000 mass ppm or less, 215 mass ppm or more and 25,000 mass ppm or less, 300 mass ppm or more and 20,000 mass ppm or less, 500 mass ppm or more and 15 ,000 mass ppm or less, and 1,000 mass ppm or more and 10,000 mass ppm or less.
• the content of methyl isobutyrate is more preferably 215 mass ppm or more and 25,000 mass ppm or less, and still more preferably 500 mass ppm or more and 15,000 mass ppm or less.
• methyl isobutyrate is thought to exhibit excellent photostability 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 methyl isobutyrate in combination with additives such as UV absorbers and HALS. By using methyl isobutyrate and the additive in combination, it is possible to provide a methacrylic resin composition and a resin molded product with increased light stability at a lower cost.
• the methacrylic resin composition may contain components other than the methacrylic polymer (P) and methyl isobutyrate within the range in which the effects of the present invention can be obtained.
• additives selected from agents, UV absorbers, and light stabilizers other than methyl isobutyrate.
• the methacrylic polymer (P) is one of the components contained in the methacrylic resin composition according to this embodiment.
• the methacrylic resin composition can improve transparency, suppress decomposition by heat and light, and improve heat moldability, heat resistance, and mechanical strength. can be made better.
• the heat resistance inherent in the methacrylic polymer (P) and the synergistic effect of methyl isobutyrate when exposed to UV for a long time, yellowing is suppressed, and photostability is improved. It is possible to obtain a methacrylic resin molded article which has high heat resistance and maintains heat resistance.
• the methacrylic polymer (P) is a copolymer containing MMA units and acrylic acid ester units (hereinafter also referred to as a methacrylic polymer (P1)), or a copolymer containing MMA units and styrene units ( Hereinafter, it is also referred to as a methacrylic polymer (P2).).
• the arrangement of these copolymers is not particularly limited, and may be, for example, random copolymers, block copolymers, alternating copolymers, etc., but random copolymers are preferred.
• the repeating unit derived from the acrylic acid ester is a repeating unit derived from the 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 copolymerizable with MMA. Examples thereof include acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and t-butyl acrylate. These may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios and combinations.
• acrylic At least one acrylate ester selected from the group consisting of methyl acid, n-ethyl acrylate, and n-butyl acrylate is preferred, and n-butyl acrylate is more preferred.
• the content of MMA units in the methacrylic polymer (P1) is not particularly limited. From the viewpoint of good heat resistance, the total mass of the methacrylic polymer (P1) is preferably 70.0% by mass or more, more preferably 80.0% by mass or more, and 90% by mass or more. It is more preferably at least 0.0% by mass, and usually at most 100% by mass.
• the content of the acrylate unit in the methacrylic polymer (P1) is not particularly limited, but from the viewpoint of good heat resistance and light stability, it is preferably 30% by mass or less. It is more preferably 10% by mass or less, more preferably 10% by mass or less, and usually 0% by mass or more.
• the above content ratio is the total content ratio of two or more kinds of acrylic acid ester units.
• the content ratio of the MMA unit in the methacrylic polymer (P2) is not particularly limited, but from the viewpoint of good heat resistance, it is 50.5% with respect to the total mass of the methacrylic polymer (P2). It is preferably 0% by mass or more, more preferably 60.0% by mass or more, still more preferably 70.0% by mass or more, and usually 100% by mass or less.
• the content of styrene units in the methacrylic polymer (P2) is not particularly limited, but from the viewpoint of good transparency, it is preferably 50% by mass or less, and 40% by mass or less. is more preferable, more preferably 30% by mass or less, and usually 0% by mass or more.
• the methacrylic polymer (P) in the present embodiment is a structural unit derived from a polyfunctional monomer containing two or more radically polymerizable functional groups in one molecule (hereinafter referred to as , referred to as “polyfunctional monomer units”).
• polyfunctional monomer units a polyfunctional monomer containing two or more radically polymerizable functional groups in one molecule
• the term "radical polymerizable functional group” as used herein refers to any group having a carbon-carbon double bond and capable of being radically polymerized. Specific examples include a vinyl group, an allyl group, a (meth)acryloyl group, A (meth)acryloyloxy group and the like can be mentioned.
• a (meth)acryloyl group is preferable from the viewpoint that the compound having a radically polymerizable functional group has excellent storage stability and that the polymerizability of the compound can be easily controlled.
• “(meth)acryloyl” indicates one or both of "acryloyl” and "methacryloyl”.
• Each radically polymerizable functional group in the monomer having two radically polymerizable functional groups may be the same or different.
• the methacrylic polymer (P) contains polyfunctional monomer units, solvent resistance, chemical resistance, etc. can be improved.
• Polyfunctional monomers include allyl methacrylate, allyl acrylate, ethylene glycol di(meth)acrylate, ethylene glycol tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and trimethylolpropane tri(meth) Examples include acrylates, but are not particularly limited to these. These may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios and combinations. Among these, the polyfunctional monomer is selected from ethylene glycol di (meth) acrylate and neopentyl glycol di (meth) acrylate from the viewpoint of better solvent resistance and chemical resistance. is more preferred, and ethylene glycol di(meth)acrylate is even more preferred.
• the weight average molecular weight (Mw) of the methacrylic polymer (P) measured by gel permeation chromatography (GPC) is not particularly limited. do not have.
• the weight average molecular weight (Mw) can be appropriately set according to the intended use of the resin molding. For example, the may be 4,000,000 or less.
• the weight average molecular weight is a value measured by gel permeation chromatography using standard polystyrene as a standard sample. Solvent resistance and chemical resistance can be improved by appropriately increasing the weight average molecular weight.
• the weight 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 type and amount of serial transfer agent.
• Methyl isobutyrate is one of the components contained in the methacrylic resin composition according to this embodiment.
• the methacrylic resin composition can suppress yellowish discoloration when exposed to UV for a long time. Furthermore, it is less expensive than conventional ultraviolet absorbers and the like, and can also suppress a decrease in photostability.
• the methacrylic resin composition according to the present embodiment may further contain at least one compound selected from the group consisting of methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate. It preferably further contains at least one compound selected from methyl and methyl 2-methylbutyrate.
• the lower limit of the total content of methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate with respect to the total mass of the methacrylic resin composition according to the present embodiment provides a methacrylic resin composition with better photostability. 20 mass ppm or more is preferable, 100 mass ppm or more is more preferable, 300 mass ppm or more is still more preferable, and 1,000 mass ppm or more is particularly preferable.
• the upper limit of the total content of methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate with respect to the total mass of the methacrylic resin composition according to the present embodiment is not particularly limited, but the heat resistance of the methacrylic resin is impaired. In terms of no, it is usually 50,000 mass ppm or less, preferably 25,000 mass ppm or less, more preferably 10,000 mass ppm or less, and 7,000 mass ppm or less. Preferably, it is particularly preferably 5,000 mass ppm or less.
• the total content of methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate is 20 mass ppm or more and 50,000 mass ppm or less, 100 mass ppm or more and 25,000 mass ppm or less, and 300 mass ppm. ppm or more and 10,000 mass ppm or less, 300 mass ppm or more and 7,000 mass ppm or less, and 1,000 mass ppm or more and 5,000 mass ppm or less.
• the total content of methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate is more preferably 100 mass ppm or more and 25,000 mass ppm or less, and more preferably 300 mass ppm or more and 7,000 mass ppm. More preferably:
• methyl isobutyrate relative to the total mass of the methacrylic resin composition methyl propionate, methyl 2-methylbutyrate, and methyl pyruvate is preferably within the range of the content of methyl isobutyrate described above.
• methacrylic resin composition Since the methacrylic resin composition according to the present embodiment contains the methacrylic polymer (P) and methyl isobutyrate, it has excellent photostability.
• a test piece made of a methacrylic resin composition (50 mm long x 50 mm wide, 3 mm thick) was subjected to the UV exposure test described below.
• the yellowness index (YI) measured according to ASTM D1925 obtained from before the start of the UV exposure test to 200 hours after the start of the UV exposure test is 5.5 or less, preferably 5.0 or less, more preferably 4.5 or less , and more preferably 4.0 or less.
• the test piece preferably has a light transmittance of 15.0% or more at a wavelength of 295 nm or a light transmittance of 35.0% or more at a wavelength of 315 nm.
• the test piece has a light transmittance of 15.0% or more at a wavelength of 295 nm and a light transmittance of 35.0% or more at a wavelength of 315 nm.
• the light transmittance is measured using a haze meter (for example, "NDH4000” manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7361-1: 1997, and the total light transmission in the thickness direction of the test piece. means rate (Tt).
• a resin molded article (also referred to simply as a "resin molded article") according to the fourth embodiment of the present invention is a resin molded article containing the methacrylic resin composition according to the third embodiment of the present invention.
• the resin molded article is not particularly limited as long as it is a molded article containing the above methacrylic resin composition, and a molded article consisting only of a methacrylic resin composition is substantially a methacrylic resin composition. and resin moldings.
• the shape of the resin molded body examples include a plate-shaped resin molded body (resin plate) and a sheet-shaped resin molded body (resin sheet).
• the thickness of the resin molding can be adjusted to any desired thickness from a thick plate to a thin film.
• the thickness can be 1 mm or more and 30 mm or less.
• the resin molding contains the methacrylic resin composition described above, it has excellent light stability. That is, a test piece of the resin molding (50 mm long ⁇ 50 mm wide, 3 mm thick) is obtained from before the start of the UV exposure test to 200 hours after the start of the UV exposure test, according to ASTM D1925. It exhibits excellent light stability such that the yellowness index (YI) as measured by
• the test strips preferably exhibit high photostability, such as a light transmission of 15.0% or greater at a wavelength of 295 nm, or a light transmission of 35.0% or greater at a wavelength of 315 nm.
• the test piece has a light transmittance of 15.0% or more at a wavelength of 295 nm and a light transmittance of 35.0% or more at a wavelength of 315 nm.
• the light transmittance is the total light transmission in the thickness direction of the test piece measured using a haze meter (for example, "NDH4000” manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7361-1: 1997. means rate (Tt).
• Method for producing methacrylic resin composition or resin molding> A method for producing a methacrylic resin composition or a resin molded article containing the resin composition (hereinafter, the methacrylic resin composition and the resin molded article are also collectively referred to as "resin composition etc.”), No special restrictions.
• the polymerizable composition (X2) according to the second embodiment of the present invention preferably 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 portion of the polymerizable composition (X2) to prepare a syrup, and a polymerization step of polymerizing the polymerizable components in the syrup.
• "polymerizing a part of the polymerizable composition (X2)" in the syrup preparation step means 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. It means that the polymerization is carried out so that the content is 60% by mass or more, more preferably 10% by mass or more and 40% by mass or less.
• the polymerization temperature for polymerizing the polymerizable composition (X2) is not particularly limited, and can be appropriately determined by those skilled in the art according to well-known techniques. Generally, 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 to be used. In addition, the polymerizable composition (X2) can be polymerized under multistage temperature conditions as necessary. The polymerization time may be appropriately determined according to the progress of polymerization and curing.
• Polymerization methods for the polymerizable composition (X2) include, for example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method and a dispersion polymerization method. Legal is preferred.
• the method for producing the resin composition or the like specifically includes, for example, a method of obtaining a resin composition or the like by a bulk polymerization method using a known cast polymerization method such as a cell casting method or a continuous casting method, or Moreover, the method of shape
• a cast polymerization method for example, when obtaining a resin composition having a plate-like shape, two glass plates or metal plates (SUS plates) facing each other and a soft resin tube or the like arranged at the edge thereof are used. Using the space formed by the gasket 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 and subjected to heat polymerization treatment to complete the polymerization. , a cell casting method in which a resin composition or the like is taken out from a mold.
• a 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 gaskets such as soft resin tubes 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, and the polymerization is completed by heat polymerization treatment,
• a continuous casting method, in which the resin composition or the like is continuously taken out from the other end of the endless belt, can be mentioned.
• a resin composition or the like having a desired thickness can be obtained by appropriately adjusting the spacing of the voids in the mold by adjusting the thickness (diameter) of the gasket.
• the thickness of the plate-shaped resin composition or the like is usually set in the range of 1 mm or more and 30 mm or less.
• resin composition, etc. are not particularly limited, but include tanning beds, lighting equipment, skin therapy equipment, medical equipment, UV irradiation devices, equipment for growing animals and plants, and skylights. , and HID lamps. More specifically, a lighting member which is a member for the purpose of daylighting used in any of tanning beds and skylights, or a lighting device, a skin therapy device, a medical device, a UV irradiation device, and for growing animals and plants It is preferably used as a translucent member which is a member intended to transmit light used in any of equipment, HID lamps, and the like.
• the monomer composition according to the first embodiment of the present invention contains methyl isobutyrate, and is a methacrylic resin composition obtained by radically polymerizing a polymerizable composition (X2) containing the monomer composition. has excellent light stability and suppresses yellowing while ensuring excellent heat resistance.
• a methacrylic resin composition in which the monomer composition according to the first embodiment of the present invention contains methyl isobutyrate, thereby ensuring excellent heat resistance, excellent light stability, and suppressed yellowing. is obtained as follows.
• Polymers containing units based on methyl methacrylate generate radical species when the main chain or side chains are cleaved by light.
• the generated radical species usually causes yellowing of the methacrylic resin and reduction in mechanical strength due to reduction in molecular weight.
• the methyl isobutyrate contained in the monomer composition according to the first embodiment of the present invention remains in the methacrylic resin composition and functions as a radical scavenger.
• the methacrylic resin composition is considered to exhibit excellent heat resistance and good light stability.
• ⁇ Photo stability ( ⁇ YI)> A metal weather super-accelerated photostability tester (Daipla ⁇ Using Wintes Co., Ltd., model name: KU-R5CI-A), a UV exposure test was performed, and according to the method described later, the change in yellowness from before the start of the UV exposure test to 200 hours after the start ( ⁇ YI) was measured.
• a test piece square shape of 50 mm long x 50 mm wide, thickness 5 mm
• the irradiation intensity of ultraviolet rays (UV) irradiated from the metal halide lamp to the test piece was measured with an ultraviolet illuminometer (manufactured by Ushio Inc., model name: UIT-101), and the irradiation intensity at a wavelength of 330 to 390 nm was 80 mW/ Corrected to be cm 2 .
• the evaluation chamber of the metal weather ultra-accelerated photostability tester is set to an environment with a temperature of 63° C.
• a spectroscopic color difference meter manufactured by Nippon Denshoku Industries Co., Ltd., model name: SE-7700 was used to measure the yellowness (yellow index: YI) of the test piece in accordance with ASTM D1925. It was measured. Using one test piece before the start of the UV exposure test and one test piece after 200 hours after the start, measurement was performed once for each test piece, and the change in the measured value was the change in yellowness ( ⁇ YI).
• Example 1 Production of syrup Methyl isobutyrate was added to a reactor (polymerization vessel) equipped with a condenser, thermometer and stirrer at a concentration of 2,000 ppm, and 98.0 parts of MMA and 2.0 parts of BA were supplied, After bubbling 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 1-dodecanethiol as a chain transfer agent were added to 0.
• Table 1 shows the evaluation results of the properties of the obtained resin moldings.
• "-" means that no measurement was performed.
• Example 2 A methacrylic resin composition and a resin molding 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.
• Table 1 shows the composition of the obtained methacrylic resin composition.
• Table 1 shows the evaluation results of the properties of the obtained resin moldings.
• Example 3 (1) Production of Syrup Methyl isobutyrate was added to a reactor (polymerization reactor) equipped with a cooling pipe, a thermometer and a stirrer at a concentration of 500 ppm, 100 parts of MMA was supplied, and nitrogen gas was bubbled with stirring. , started heating. When the internal temperature of the reactor reached 80°C, 0.12 parts of 2,2'-azobis-(2,4-dimethylvaleronitrile) was added as a radical polymerization initiator, and further the internal temperature of the reactor increased. After heating to 100° C., it was held for 9 minutes. Then, the reactor was cooled until the internal temperature reached room temperature to obtain a syrup. The polymer content in the syrup was 20% by weight relative to the total weight of the syrup.
• Table 1 shows the evaluation results of the properties of the obtained resin moldings.
• "-" means that no measurement was performed.
• Examples 4 to 7 A methacrylic resin composition and a resin molding were produced in the same manner as in Example 3, except that the composition of the monomer composition was changed as shown in Table 1.
• Table 1 shows the composition of the obtained methacrylic resin composition.
• Table 1 shows the evaluation results of the properties of the obtained resin moldings.
• Example 3 A methacrylic resin composition and a resin molding were produced in the same manner as in Example 3, except that the composition of the monomer composition was changed as shown in Table 1.
• Table 1 shows the composition of the obtained methacrylic resin composition.
• Table 1 shows the evaluation results of the properties of the obtained resin moldings.

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