WO2017164120A1 - （メタ）アクリル系樹脂組成物、樹脂成形体、樹脂積層体及び（メタ）アクリル系樹脂組成物の製造方法 - Google Patents

（メタ）アクリル系樹脂組成物、樹脂成形体、樹脂積層体及び（メタ）アクリル系樹脂組成物の製造方法 Download PDF

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WO2017164120A1
WO2017164120A1 PCT/JP2017/010924 JP2017010924W WO2017164120A1 WO 2017164120 A1 WO2017164120 A1 WO 2017164120A1 JP 2017010924 W JP2017010924 W JP 2017010924W WO 2017164120 A1 WO2017164120 A1 WO 2017164120A1
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meth
mass
acrylic
resin composition
acrylic resin
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PCT/JP2017/010924
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English (en)
French (fr)
Japanese (ja)
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正浩 中野
石原　豊
正法 鈴木
博之 渡辺
小澤　覚
百瀬　扶実乃
小亀　朗由
佑太 前中
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三菱ケミカル株式会社
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Priority to CN201780018937.3A priority Critical patent/CN108884289A/zh
Priority to JP2017517141A priority patent/JP6489210B2/ja
Publication of WO2017164120A1 publication Critical patent/WO2017164120A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • 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

Definitions

  • the present invention relates to a (meth) acrylic resin composition, a resin molded body, a resin laminate, and a method for producing the (meth) acrylic resin composition.
  • This application is filed in Japanese Patent Application No. 2016-059809 filed on March 24, 2016, Japanese Patent Application No. 2016-070516 filed on March 31, 2016, Japanese Patent Application No. Priority based on Japanese Patent Application No. 2016-082736 filed on April 19, 2016, Japanese Patent Application No. 2016-083664 filed in Japan, and Japanese Patent Application No. 2017-018218 filed on February 2, 2017 Claim the right and use it here.
  • (Meth) acrylic resin based on methyl methacrylate is excellent in transparency, heat resistance and weather resistance, and has balanced performance in mechanical strength, thermal properties, moldability, etc. ing. Therefore, it is used for many uses, such as a lighting material, an optical material, a signboard, a display, a decoration member, a building member, and flame retardance and heat resistance are calculated
  • a flame retardant is added to impart flame retardancy to a (meth) acrylic resin, there is a problem that transparency and heat resistance are lowered. Thus, studies have been made to impart flame retardancy without impairing this.
  • Patent Document 1 proposes a flame-retardant methacrylic resin plate comprising a methacrylic resin containing a monomer having an alicyclic hydrocarbon group in the side chain and a halogenated phosphate ester. Discloses dicyclopentanyl methacrylate as a monomer having an alicyclic hydrocarbon group in the side chain.
  • Patent Document 2 and Patent Document 3 propose a (meth) acrylic polymer containing methyl methacrylate and isobornyl (meth) acrylate, and a flame retardant methacrylic resin plate containing a phosphorus compound as a flame retardant. ing.
  • JP 2011-046835 A Japanese Patent Laying-Open No. 2015-086250 International Publication No. 2016/063898
  • the first object of the present invention is to provide a (meth) acrylic resin composition having good heat resistance and higher flame retardancy, and a resin molded article comprising the (meth) acrylic resin composition. It is to provide.
  • the second object of the present invention is to provide a method for stably producing the (meth) acrylic resin composition.
  • a third object of the present invention is to provide a resin molded article having high flame retardancy and further high impact resistance, and a (meth) acrylic resin composition for producing the resin molded article. is there.
  • a fourth object of the present invention is to provide a resin molded article having high flame retardancy and further high scratch resistance, and a (meth) acrylic resin composition for producing the resin molded article. is there.
  • the said (meth) acrylic-type resin composition is 5.0 to 35.0 mass parts of said phosphorus flame retardant (C) with respect to 100 mass parts of said (meth) acrylic-type polymers (P).
  • the (meth) acrylic resin composition contains the amphiphilic compound (E) in an amount of 0.01 parts by mass or more and 2.0 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (P).
  • the (meth) acrylic polymer (P) is derived from a (meth) acrylic acid ester (M) having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain.
  • the (meth) acrylic resin composition according to [1] which is a polymer containing a repeating unit.
  • the (meth) acrylic polymer (P) has a repeating unit derived from a (meth) acrylic acid ester (M) having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain.
  • a polymer containing, In the (meth) acrylic resin composition, the phosphorous flame retardant (C) has a dispersed particle diameter of 0.8 ⁇ m or less, and within 3 minutes in the flame resistance test A method of JIS K 6911-1995.
  • a (meth) acrylic resin composition having self-extinguishing flame retardancy.
  • the phosphorous flame retardant (C) is 5.0 parts by mass or more and 35.0 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (P).
  • the phosphorus-based flame retardant (C) is at least one selected from a halogen-containing phosphate ester and a halogen-containing phosphonate ester, and the amphiphilic compound (E) is represented by the following chemical formula (I).
  • R represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an alkyl carboxyl group, an alkylene group, a cycloalkylene group, an arylene group, an arylalkylene group, or a polyoxyalkylene group.
  • N is 1 or 2.
  • (Meth) acrylic resin composition [11]
  • the (meth) acrylic polymer (P) is a repeating unit derived from the (meth) acrylic acid ester (M).
  • a monomer in which the (meth) acrylic polymer (P) has two or more ethylenically unsaturated bonds in the molecule with respect to the total mass of the (meth) acrylic polymer (P) ( The (meth) acrylic resin composition according to [10] or [11], which is a polymer containing 0.05 to 0.40 mass% of structural units derived from B). [13] The half width of the peak of the decomposition product of the repeating unit derived from the (meth) acrylic acid ester (M), measured by the following measuring method 1, is 26 ° C. or less, from [2] to [12] The (meth) acrylic resin composition according to any one of the above.
  • ⁇ Measurement method 1> Using a generated gas analysis measurement device (EGA-MS), 2 mg of a (meth) acrylic resin composition was generated in a helium atmosphere (flow rate 20 ml / min) at a heating rate of 10 ° C./min. Mass analysis of the gas is performed, and the half-value width of the decomposition product peak in the obtained temperature-chromatogram curve is obtained.
  • EVA-MS generated gas analysis measurement device
  • the generation temperature of the decomposition product of the repeating unit derived from the (meth) acrylic acid ester (M) obtained by the following measurement method 2 and the generation temperature of the decomposition product of the phosphorus flame retardant (C) are The (meth) acrylic resin composition according to any one of [2] to [13], wherein the following formula (1) is satisfied.
  • Tc generation temperature of phosphorus flame retardant (C) decomposition product (unit: ° C.)
  • Tm Generation temperature of a decomposition product of a repeating unit derived from (meth) acrylic acid ester (M) (unit: ° C.)
  • GAA-MS generated gas analysis measurement device
  • the generation temperature of the decomposition product of the repeating unit derived from the (meth) acrylic acid ester (M) obtained by the measurement method 2 and the generation temperature of the decomposition product of the repeating unit derived from the methyl methacrylate are as follows:
  • D 1 (%)
  • the (meth) acrylic resin composition is selected from the following multi-structure acrylic copolymer particles (D1) or acrylic block copolymer (D2): The (meth) acrylic resin composition according to any one of [1] to [19], comprising (D).
  • Acrylic block copolymer (D2) Methacrylic acid ester polymer block (d2-1) 10% by mass to 60% by mass and Acrylic ester polymer block (d2-2) 40% by mass to 90% by mass Block copolymer.
  • the impact resistance improver (D) is 2.0 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (P) in the (meth) acrylic resin composition.
  • a resin molded article comprising the (meth) acrylic resin composition according to any one of [1] to [22].
  • a sheet-shaped resin laminate comprising a cured film (F) on at least one surface of the resin molded body according to [23], Curability in which the cured film (F) contains a polyfunctional monomer (F1) having three or more (meth) acryloyl groups and a polyfunctional monomer (F2) having two (meth) acryloyl groups.
  • a resin laminate comprising a cured product of the composition (f).
  • the curable composition (f) contains 50% by mass to 80% by mass of the polyfunctional monomer (F1) and 20% by mass to 50% by mass of the polyfunctional monomer (F2).
  • Step 1 A monomer composition (X1) containing a (meth) acrylic acid ester (M) monomer having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain and a parent A step of obtaining a polymerizable composition (X3) by adding a phosphorus-based flame retardant (C) to a mixture (X2) containing a medicinal compound (E).
  • Step 2 A step of polymerizing the polymerizable composition (X3).
  • [27] The method for producing the (meth) acrylic resin composition according to any one of [20] to [22], wherein in the step 1, the mixture (X2) is an amphiphilic compound ( E) and at least one type of impact resistance improver (D) selected from multi-structure acrylic copolymer particles (D1) or acrylic block copolymers (D2) ( A method for producing a (meth) acrylic resin composition.
  • Multi-structure acrylic copolymer particle (D1) a multi-layer structure having a structure in which a hard resin layer (d1-2) is formed on the surface of an elastomer particle (d1-1) containing a rubbery copolymer having a crosslinked structure Structure acrylic copolymer particles.
  • Acrylic block copolymer (D2) Methacrylic acid ester polymer block (d2-1) 10% by mass to 60% by mass and Acrylic ester polymer block (d2-2) 40% by mass to 90% by mass Block copolymer.
  • the monomer composition (X1) has a methyl methacrylate monomer content of 19.95% by mass or more and 84.95% by mass or less based on the total mass of the monomer composition (X1).
  • the monomer composition (X1) is, as the (meth) acrylic acid ester (M), A methacrylic acid ester (M1) having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain; An acrylic ester (M2) having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain, and The methacrylic acid ester (M1) is 10.0% by mass or more and 79.5% by mass or less, The manufacturing method of the (meth) acrylic-type resin composition as described in [28] whose said acrylic ester (M2) is 0.50 mass% or more and 20.0 mass% or less.
  • the monomer composition (X1) contains 0.05% by mass or more and 0.40% by mass or less of the monomer (B) having two or more ethylenically unsaturated bonds in the molecule. 28] or the method for producing a (meth) acrylic resin composition according to [29]. [31] Any one of [26] to [30], wherein the monomer composition (X1) includes in advance a polymer (P1) containing a repeating unit derived from the (meth) acrylic acid ester (M). The manufacturing method of the (meth) acrylic-type resin composition as described in a term.
  • the polymerizable composition (X3) includes the monomer composition (X1) as 100 parts by mass and the phosphorus flame retardant (C) in an amount of 5.0 parts by mass to 35.0 parts by mass.
  • the present invention it is possible to stably provide a (meth) acrylic resin composition having good heat resistance and further high flame retardancy, and a resin molded body comprising the (meth) acrylic resin composition. it can. Moreover, according to the present invention, it is possible to stably provide a (meth) acrylic resin composition having high flame retardancy and high impact resistance, and a resin molded article comprising the (meth) acrylic resin composition. In addition, according to the present invention, it is possible to stably provide a (meth) acrylic resin composition having high flame retardancy and high scratch resistance, and a resin molded body comprising the (meth) acrylic resin composition. Such a resin molded body is suitable for applications requiring high flame retardancy such as signboards.
  • (meth) acrylate and “(meth) acrylic acid” are each at least one selected from “acrylate” and “methacrylate”, and at least one selected from “acrylic acid” and “methacrylic acid”. Means.
  • “monomer” means an unpolymerized compound
  • “repeating unit” means a unit derived from the monomer formed by polymerization of the monomer.
  • the repeating unit may be a unit directly formed by a polymerization reaction, or a part of the unit converted into another structure by treating a polymer.
  • mass% indicates the content of a predetermined component contained in the total amount of 100 mass%.
  • ⁇ (Meth) acrylic resin composition As an example of an embodiment of the (meth) acrylic resin composition of the present invention, a (meth) acrylic polymer (P) described later, a phosphorus flame retardant (C) described later, and an amphiphilic compound (E) described later.
  • a (meth) acrylic resin composition containing a (meth) acrylic polymer (P), a phosphorus flame retardant (C) described later, and an amphiphilic compound (E) described later.
  • the (meth) acrylic polymer (P) is a polymer containing a repeating unit derived from the (meth) acrylic acid ester (M) described later.
  • the dispersion particle size of the phosphorus-based flame retardant (C) is 0.8 ⁇ m or less, and has a flame retardancy that self-extinguishes within 3 minutes in the flame resistance test A method of JIS K 6911-1995. It is an acrylic resin composition.
  • the (meth) acrylic resin composition has flame retardancy that self-extinguishes within 3 minutes in the above test, it is preferable from the viewpoint of safety because it can prevent the spread of fire and fires in the event of a fire, and sign such as a gas station Suitable for use on signboards.
  • the said (meth) acrylic-type polymer (P) can be made into the polymer containing the repeating unit derived from the (meth) acrylic acid ester (M) mentioned later.
  • a (meth) acrylic-type resin composition contains a phosphorus flame retardant as one of the structural components.
  • the upper limit of the dispersed particle size of the phosphorus-based flame retardant is not particularly limited, but is preferably 0.8 ⁇ m or less, more preferably 0.1 ⁇ m or less, because the flame retardancy of the resin molded article becomes favorable. Preferably, it is 0.05 ⁇ m or less.
  • the lower limit of the dispersed particle size is not particularly limited, and the smaller the dispersed particle size, the better.
  • Examples of the method for controlling the dispersed particle size of the phosphorus-based flame retardant (C) include, for example, the type or content of the amphiphilic compound, the type of the (meth) acrylic acid ester (M), and a later-described (meta) ) Adjusting the timing of adding the amphiphilic compound (E) and the phosphorus-based flame retardant (C) described in the method for producing an acrylic resin composition.
  • the dispersed particle size can be obtained by a method for measuring the dispersed particle size described later.
  • the dispersed particle size means the primary particle size of the dispersed particles or the secondary particle size of the aggregated particles for any 20 dispersed particles or aggregated particles observed at a magnification of 1000 times using an optical microscope. It is the value measured and averaged.
  • said aggregated particle means the secondary particle formed when the dispersed particle (primary particle) contacted.
  • the phosphorus-based flame retardant (C) is preferably 5.0 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic polymer (P). It can contain 35.0 mass parts or less, More preferably, 10.0 mass parts or more and 30.0 mass parts or less, More preferably, 15.0 mass parts or more and 25.0 mass parts or less can be contained.
  • the flame retardancy of the resin molded article becomes good.
  • the upper limit of the content of the phosphorus-based flame retardant (C) with respect to 100 parts by mass of the (meth) acrylic polymer is 35.0 parts by mass or less, the heat resistance of the resin molded body is good.
  • Examples of the phosphoric flame retardant (C) include a phosphoric ester compound (hereinafter abbreviated as “phosphoric ester”) and a phosphonic ester compound (hereinafter abbreviated as “phosphonic ester”). Can do. Specifically, the following compounds can be exemplified, but are not limited thereto. These compounds can be used alone or in combination of two or more.
  • Halogen-free phosphate ester Monoethyl phosphate, monobutyl phosphate, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tricres Aromatic phosphate esters such as dilphosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), and their derivative compounds, and condensates thereof.
  • TMP trimethyl phosphate
  • TXP triethyl phosphate
  • TXP cresyl diphenyl phosphate
  • EHDP 2-ethylhexyl diphenyl phosphate
  • aromatic condensed phosphate esters such as resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A bis-diphenyl phosphate, and derivatives thereof, and condensates thereof.
  • Halogen-containing phosphate esters tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, bis (2,3-dibromopropyl) -2 , 3-dichloropropyl phosphate, bis (chloropropyl) octyl phosphate, etc., and their derivative compounds, and their condensates.
  • Phosphonic acid ester dimethyl vinyl phosphonate, diethyl vinyl phosphonate, diphenyl vinyl phosphonate, diphenyl vinyl phosphine oxide, etc., and their derivative compounds, and their condensates.
  • halogen-free phosphate ester examples include “JAMP-2”, “JAMP-4”, “JAMP-8”, “JAMP-12”, “JP-501”, “JP” manufactured by Johoku Chemical Co., Ltd. -502 ",” JP-504 “,” JP-504A “,” JP-506H “,” JP-508 “,” JP-512 “,” JP-513 “,” JP-518O “,” JP-524R “ ”,“ DBP ”,“ LB-58 ”,“ TMP ”,“ TEP ”,“ TPP ”,“ TCP ”,“ TXP ”,“ CDP ”,“ PX-110 ”manufactured by Daihachi Chemical Industry Co., Ltd.
  • phosphonic acid ester for example, commercially available products such as “V series” manufactured by Katayama Chemical Co., Ltd. and “Nonen 73” manufactured by Maruhishi Oil Chemical Co., Ltd. can be used.
  • the phosphorus-based flame retardants (C) described above at least one selected from a phosphate ester and a phosphonate ester is easily suppressed by the amphiphilic compound (E), and as a result, resin molding is performed. It is preferable because the flame retardancy of the body becomes good.
  • Specific examples of the phosphate ester include halogen-containing phosphate esters. Resin due to a synergistic effect of the phosphorus-based flame retardant (C) having the effect of improving flame retardancy, the repeating unit derived from the (meth) acrylic acid ester (M) and the structural unit derived from the monomer (B) described later The flame retardancy of the molded product can be improved.
  • the (meth) acrylic resin composition in the present invention contains an amphiphilic compound (E) as one of the constituent components.
  • an amphiphilic compound (E) As one of the constituent components.
  • the amphiphilic compound refers to a compound having both a “hydrophilic group” and a “hydrophobic group (lipophilic group)” in one molecule.
  • the “hydrophilic group” means a site having higher affinity for the phosphorus-based flame retardant (C) than the (meth) acrylic polymer (P) described later.
  • Oil group refers to a site having higher affinity for the (meth) acrylic polymer (P) than the phosphorus flame retardant (C). Although the reason why the flame retardancy of the resin molded product is excellent by including the amphiphilic compound is not clear, the hydrophilic group portion of the amphiphilic compound is easily coordinated to the phosphorus-based flame retardant (C). Since the hydrophobic group (lipophilic group) site is easily coordinated to the (meth) acrylic polymer (P), the phosphorus-based flame retardant (C) does not form aggregated particles, and the resin composition is uniformly fine. This is presumed to be easily dispersed or dissolved.
  • the lower limit of the content of the amphiphilic compound (E) is not particularly limited, but the phosphorus-based flame retardant (C) does not form aggregated particles, and the flame retardancy of the resin molded article is improved. Therefore, 0.01 part by mass or more is preferable, 0.05 part by mass or more is more preferable, and 0.1 part by mass or more is more preferable with respect to 100 parts by mass of the (meth) acrylic polymer (P).
  • the lower limit of the content of the amphiphilic compound (E) is not particularly limited, but is preferably 2.0 parts by mass or less, because the flame retardancy of the resin molded article can be maintained well, and is 0.6 mass. Part or less is more preferable, and 0.3 part by weight or less is more preferable.
  • the flame retardancy of the resin molded product can be further improved by using an anionic surfactant as the amphiphilic compound (E).
  • the anionic surfactant refers to a compound having a structurally anionic hydrophilic group.
  • the anionic hydrophilic group portion of the anionic surfactant is easily coordinated by the phosphorus flame retardant (C). It is presumed that the system flame retardant (C) does not form aggregated particles and is easily finely dispersed or dissolved by the resin composition.
  • amphiphilic compound (E) an anionic surfactant is described.
  • a nonionic surfactant or Of course, it is possible to use an anionic surfactant.
  • carboxylate, sulfonate, sulfate ester salt, and the like can be used as the anionic surfactant.
  • the flame retardance of the resin molding can be made more excellent by using the alkali metal salt of alkyl sulfosuccinic acid.
  • the flame retardancy of the resin molding can be further improved by using sodium dioctyl sulfosuccinate as the alkali metal salt of the alkyl sulfosuccinic acid.
  • the phosphorus-based flame retardant (C) is at least one selected from halogen-containing phosphates and halogen-containing phosphonates
  • the amphiphilic compound (E) is represented by the following chemical formula:
  • R represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an alkyl carboxyl group, an alkylene group, a cycloalkylene group, an arylene group, an arylalkylene group, or a polyoxyalkylene group.
  • N is 1 or 2.
  • the amphiphilic compound (E) represented by the chemical formula (I) can be obtained by changing R in the formula (I) to an aliphatic alkyl group having 2 to 24 carbon atoms. Since the effect of improving the dispersibility of the phosphorus-based flame retardant (C) possessed by is improved, the flame retardancy of the resin molded product can be further improved.
  • the (meth) acrylic resin composition in the present invention contains the following (meth) acrylic polymer (P) as one of the constituent components.
  • the (meth) acrylic polymer (P) as one of the constituent components, a (meth) acrylic resin molding excellent in heat resistance and flame retardancy due to a synergistic effect with other constituent components described later.
  • the body can be obtained.
  • the (meth) acrylic polymer (P) includes a repeating unit derived from (meth) acrylic acid ester (M) having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain.
  • a polymer can be used.
  • the (meth) acrylic polymer (P) contains a repeating unit derived from the (meth) acrylic acid ester (M)
  • the flame retardancy of the resin molded body is improved and the above-mentioned amphiphilic substance (E).
  • action it can suppress that a phosphorus flame retardant (C) forms an aggregated particle.
  • the (meth) acrylic polymer (P) a repeating unit derived from methyl methacrylate, a repeating unit derived from the (meth) acrylic acid ester (M), and two or more molecules in the molecule described later.
  • the structural unit derived from the monomer (B) having an ethylenically unsaturated bond can be included. Since the (meth) acrylic polymer (P) contains a repeating unit derived from methyl methacrylate, the resin molded article has excellent heat resistance and weather resistance, and more mechanical strength, thermal properties, and moldability. It can be excellent. When the (meth) acrylic polymer (P) contains the structural unit derived from the monomer (B), the flame retardancy, heat resistance, and mechanical properties of the resin molded product can be further improved.
  • the lower limit of the content of the repeating unit derived from methyl methacrylate is not particularly limited, but is preferably 19.95% by mass or more because the impact resistance and mechanical strength of the resin molded article are good. More preferably, it is more preferably 5% by mass or more.
  • the upper limit of the content is not particularly limited, but is preferably 84.95% by mass or less, more preferably 82.0% by mass or less, and 79.79% by mass because the flame retardancy of the resin molded article is improved. 1% by mass or less is more preferable. Said upper limit and lower limit can be arbitrarily combined in the range which does not exceed 100 mass% of total mass of (meth) acrylic-type polymer (P).
  • the (meth) acrylic acid ester (M) is a monofunctional (meth) acrylic acid ester having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain. .
  • the flame retardancy of the resin molded product becomes good.
  • Specific examples include cyclohexyl (meth) acrylate, bornyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, and methacrylic acid.
  • the repeating unit derived from the (meth) acrylic acid ester (M) has a bulky side chain, and this bulky side chain is eliminated by decomposition to generate a volatile component, thereby generating oxygen in the combustion field.
  • the concentration decreases, and the flame retardancy of the resin composition becomes excellent.
  • This bulky side chain decomposition can be promoted, for example, using thermal energy from combustion.
  • the above-mentioned phosphorus-based flame retardant (C) is added to the resin composition, the decomposition product of the phosphorus-based flame retardant (C) promotes the decomposition of the bulky side chain, and the resin composition becomes difficult. The flammability can be improved.
  • the half-value width of the peak of the decomposition product of the repeating unit derived from the (meth) acrylic acid ester (M) measured by the following measurement method 1 (hereinafter simply referred to as “reduced product”).
  • the flame retardancy of the body can be made excellent.
  • the half width of the peak of the decomposition product is more preferably 21 ° C. or less, and further preferably 19 ° C. or less.
  • the lower limit of the half-value width of the peak of the decomposition product is not particularly limited, but is preferably 5 ° C or higher and more preferably 10 ° C or higher.
  • ⁇ Measurement method 1> Using a generated gas analysis measurement device (EGA-MS), 2 mg of a (meth) acrylic resin composition was generated in a helium atmosphere (flow rate 20 ml / min) at a heating rate of 10 ° C./min. Mass analysis of the gas is performed, and the half-value width of the decomposition product peak in the obtained temperature-chromatogram curve is obtained.
  • EVA-MS generated gas analysis measurement device
  • the half width of the peak of the decomposition product is the type of monomer unit constituting the (meth) acrylic polymer (P), the content of the monomer unit, the type and content of the phosphorus flame retardant (C). It can be controlled by adjusting the amount.
  • the repeating unit derived from the (meth) acrylic acid ester (M) in the (meth) acrylic polymer (P) obtained by the following measurement method 2.
  • calculated from the generation temperature Tc (unit: ° C.) of the decomposition product of T and the generation temperature Tm (unit: ° C.) of the decomposition product of the phosphorus flame retardant (C) is (meta ) An index representing the ease of generation of decomposition (desorption) gas of the acrylic resin composition. The smaller this value, the better the flame retardancy of the (meth) acrylic resin composition.
  • can be controlled by selecting the types of (meth) acrylic acid ester (M) and phosphorus flame retardant (C).
  • the generation temperature of the decomposition product of the repeating unit derived from the (meth) acrylic acid ester (M) and the decomposition product of the phosphorus flame retardant (C) is expressed by the following formula (1).
  • filling the flame retardance and heat resistance of a resin molding can be made more favorable.
  • is preferably 40 or less, because the flame retardancy of the resin molded article becomes good, more preferably 20 or less, and even more preferably 10 or less.
  • is not particularly limited as long as it exceeds 0.
  • Tc generation temperature of phosphorus flame retardant (C) decomposition product (unit: ° C.)
  • Tm Generation temperature of a decomposition product of a repeating unit derived from (meth) acrylic acid ester (M) (unit: ° C.)
  • ⁇ Measurement method 2> Using a generated gas analysis measurement device (EGA-MS), 2 mg of (meth) acrylic resin composition was generated in a helium atmosphere (flow rate 20 ml / min) at a heating rate of 10 ° C./min. And the generation temperature of the decomposition product in the obtained temperature-chromatogram curve is determined.
  • EVA-MS generated gas analysis measurement device
  • the value of “Ta-Tm” (unit: ° C.) is the repeating unit derived from methyl methacrylate, which is the main decomposition product of the (meth) acrylic resin composition
  • Ta-Tm The larger the value of “Ta-Tm”, the more the decomposition product of the repeating unit derived from methyl methacrylate, which is the main decomposition product of the (meth) acrylic resin composition, is generated. Since the decomposition product derived from the side chain in the repeating unit derived from the acrylate ester (M) is generated, the flame retardancy of the resin molded article is improved.
  • Ta-Tm is determined appropriately depending on the copolymer composition of the (meth) acrylic polymer (P), the type and molecular weight of the (meth) acrylic acid ester (M), and the type of additives such as a crosslinking agent. Can be selected and controlled.
  • the “main decomposition product of the (meth) acrylic resin composition” excludes the decomposition product derived from the side chain in the repeating unit derived from the (meth) acrylic acid ester (M). It refers to a decomposition product of an acrylic resin composition.
  • the generation temperature of the decomposition product of the repeating unit derived from the (meth) acrylic acid ester (M) and the decomposition product of the repeating unit derived from the methyl methacrylate is represented by the following formula (2). It satisfies.
  • the lower limit of “Ta—Tm” is not particularly limited, but if it is 100 or more, it is preferable because the flame retardancy of the resin molded article is good, 110 or more is more preferable, and 115 or more is more preferable.
  • Ta-Tm The upper limit of “Ta-Tm” is not particularly limited, but the temperature at which the side chain of the repeating unit derived from (meth) acrylic acid ester (M) decomposes and desorbs is lowered, resulting in incombustibility. 200 or less is preferable in order to prevent it being sufficient. 100 ⁇ Ta ⁇ Tm (2) Ta: Temperature at which decomposition products of repeating units derived from methyl methacrylate are generated (unit: ° C)
  • the minimum of content of the repeating unit derived from (meth) acrylic acid ester (M) is not specifically limited, Since the flame retardance of a resin molding becomes favorable, 3.6 mass% or more is preferable, and 15.0 More preferably, it is more preferably at least 20.5% by mass.
  • the upper limit of the content is not particularly limited, but is preferably 80.0% by mass or less, more preferably 60.0% by mass or less, and more preferably 40.0% by mass because the impact resistance and mechanical strength of the resin molded article are improved. The following is more preferable. Said upper limit and lower limit can be arbitrarily combined in the range which does not exceed 100 mass% of total mass of (meth) acrylic-type polymer (P).
  • Examples of the (meth) acrylic polymer (P) containing the (meth) acrylic acid ester (M) include an aromatic hydrocarbon or an alicyclic hydrocarbon having 3 to 20 carbon atoms in the side chain.
  • a (meth) acrylic polymer comprising a repeating unit derived from (M1) and a repeating unit derived from an acrylate ester (M2) having an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain Combined (P) can be used.
  • the methacrylic acid ester (M1) and the acrylic acid ester (M2) interact with the phosphorus flame retardant (C) to synergistically enhance the flame retardant improvement effect of the phosphorus flame retardant (C). Since it has, the flame retardance of a resin molding can be improved.
  • the (meth) acrylic polymer (P) containing the (meth) acrylic acid ester (M) is 10.0% by mass or more and 79.5% by mass or less of the repeating unit derived from the methacrylic acid ester (M1). And 0.50% by mass or more and 20.0% by mass or less of the repeating unit derived from the acrylic ester (M2), and the repeating unit derived from the methacrylate (M1) and the acrylic ester (M2)
  • a (meth) acrylic polymer (P) containing 15.0% by mass or more and 80.0% by mass or less of the repeating units can be used.
  • the minimum of content of the repeating unit derived from a methacrylic acid ester (M1) is not specifically limited, 10.0 mass% or more is preferable from the flame retardance and heat resistance of a resin molding becoming favorable, and 20.0 mass % Or more is more preferable. Moreover, although it does not specifically limit about the upper limit of content, since the weather resistance of a resin molding becomes favorable, 79.5 mass% or less is preferable and 70.0 mass% or less is more preferable. The above upper limit value and lower limit value can be arbitrarily combined.
  • the minimum of content of the repeating unit derived from an acrylate ester (M2) is not specifically limited, 0.50 mass% or more is preferable and 1.0 mass is preferable since the flame retardance and weather resistance of a resin molding become favorable. % Or more is more preferable.
  • the upper limit of content is not specifically limited, Since the heat resistance of a resin molding becomes favorable, 20 mass% or less is preferable and 6.0 mass% or less is more preferable. The above upper limit value and lower limit value can be arbitrarily combined.
  • the lower limit of the total content of the repeating unit derived from the methacrylic acid ester (M1) and the repeating unit derived from the acrylate ester (M2) is not particularly limited. However, the flame retardancy of the resin molded article becomes good. 0 mass% or more is preferable and 20.5 mass% or more is more preferable.
  • the upper limit of content is not specifically limited, Since the heat resistance and weather resistance of a resin molding become favorable, 80.0 mass% or less is preferable and 40.0 mass% or less is more preferable. The above upper limit value and lower limit value can be arbitrarily combined.
  • the methacrylic acid ester (M1) is at least one selected from cyclohexyl methacrylate and isobornyl methacrylate from the viewpoint of excellent effects of improving flame retardancy and heat resistance. Can be used.
  • the acrylic acid ester (M2) is at least one selected from cyclohexyl acrylate and isobornyl acrylate from the viewpoint of excellent effects of improving flame retardancy and weather resistance. (Hereinafter, “monomer (m2)”) can be used.
  • polymerization can be reduced more, and the weather resistance of resin molding becomes more favorable. Furthermore, since the monomer (m2) interacts with the phosphorus flame retardant (C) and has the effect of synergistically enhancing the flame retardant improvement effect of the phosphorus flame retardant (C), the resin molded body Can improve the flame retardancy.
  • the minimum of content of a monomer (m2) is not specifically limited, By setting it as 1.0 mass% or more with respect to 100 mass parts of said (meth) acrylic-type polymers (P).
  • the flame retardancy and weather resistance of the resin molded body can be improved, 2.0% by mass or more is more preferable.
  • the upper limit of the content is not particularly limited, but if the content is 4.99% by mass or less, it is preferable because the heat resistance of the resin molded body can be further improved, and 4.0% by mass or less is more preferable. preferable.
  • the above upper limit value and lower limit value can be arbitrarily combined.
  • the monomer (B) is a monomer having two or more vinyl groups and is one of the components of the (meth) acrylic resin composition of the present invention.
  • the flame retardancy of the resin molded product can be further improved.
  • the (meth) acrylic polymer (P) contains the structural unit derived from the monomer (B), the flame retardancy, heat resistance, and mechanical properties of the resin molded product can be further improved.
  • the minimum of content of the structural unit derived from the said monomer (B) is not specifically limited, 0.05 mass part or more is preferable from the flame retardance of a resin molding becoming favorable, 0.12 mass part or more Is more preferable.
  • the upper limit of content is not specifically limited, 0.40 mass part or less is preferable from the impact resistance and mechanical strength of a resin molding becoming favorable, and 0.36 mass part or less is more preferable. Said upper limit and lower limit can be arbitrarily combined in the range which does not exceed 100 mass% of total mass of (meth) acrylic-type polymer (P).
  • the monomer (B) is preferably a bifunctional (meth) acrylate.
  • the monomer having 10 to 14 carbon atoms has good handleability of raw materials, so that workability when producing a (meth) acrylic resin composition is improved. it can.
  • the flame retardancy of the resin molded product is improved. It is preferable because it can be made more excellent.
  • a monomer copolymerizable with methyl methacrylate and (meth) acrylic acid ester (M) is added to 100% by mass of (meth) acrylic polymer (P). It can be contained in the acrylic polymer (P) in the range of 0% by mass to 12% by mass, preferably 0.8% by mass to 9.0% by mass.
  • Monomers copolymerizable with methyl methacrylate and (meth) acrylic acid ester (M) include ethyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, (meth) I-Butyl acrylate, n-butyl (meth) acrylate, (meth) acrylic acid, maleic acid, itaconic acid and other unsaturated carboxylic acids, maleic anhydride, itaconic anhydride and other acid anhydrides, N-phenylmaleimide , Maleimide derivatives such as N-cyclohexylmaleimide, vinyl esters such as vinyl acetate and vinyl benzoate, vinyl chloride, vinylidene chloride and their derivatives, nitrogen-containing monomers such as methacrylamide and acrylonitrile, glycidyl acrylate (meth) acrylate Epoxy group-containing monomers such as styrene, ⁇ -methyl
  • MC ( ⁇ ) and MP ( ⁇ ) are relaxation spectrum intensities observed with a solid-state NMR measurement apparatus using a spin-lock cross polarization method, and can be measured by the method described later.
  • D 1 (%)
  • the carbon of the carbonyl group in the (meth) acrylic resin composition is the carbon of the carbonyl group in the ester side chain adjacent to the ⁇ carbon in the (meth) acrylic polymer (P). More specifically, in the repeating unit derived from methyl methacrylate, the repeating unit derived from the methacrylic ester (M1) or the repeating unit derived from the methacrylic ester (M2) in the (meth) acrylic polymer (P). This is the carbon of the carbonyl group in the side chain of an alicyclic hydrocarbon group having 3 to 20 carbon atoms and an aromatic hydrocarbon group adjacent to the ⁇ carbon.
  • the phosphorus atom of the phosphorus-based flame retardant (C) is a phosphorus atom of a phosphoric acid group when the phosphorus-based flame retardant (C) is a phosphate ester, and a phosphorus atom of a phosphonic acid group when the phosphorus flame retardant (C) is a phosphonate ester. .
  • the weight average molecular weight of the phosphoric acid ester and the phosphonic acid ester is 200 because the phosphoric flame retardant (C) is uniformly dissolved or finely dispersed without being localized in the (meth) acrylic resin composition. More than 500 is preferable.
  • the peak corresponding to carbon of the carbonyl group of the (meth) acrylic resin composition varies depending on the configuration of the (meth) acrylic resin composition.
  • the (meth) acrylic polymer (P) may be aromatic.
  • a polymer containing a repeating unit derived from a (meth) acrylic acid ester (M) having a hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain is used, a 13 C nuclear relaxation spectrum is used. In the vicinity of -180 ppm to -160 ppm.
  • Peaks corresponding to the phosphorus atom of the phosphorus-based flame retardant (C) varies depending on the type of phosphorus-based flame retardant (C), for example, when the phosphoric acid ester or phosphonic acid ester, of 31 P nuclear relaxation spectrum -10 Observed around ⁇ 10 ppm.
  • MC ( ⁇ ) is a numerical value that reflects the mobility of the molecules that make up the (meth) acrylic polymer (P), and MP ( ⁇ ) reflects the mobility of the molecules that make up the phosphorus flame retardant (C). It is a numerical value.
  • the phosphorus flame retardant (C) is dissolved or finely dispersed in the domain of 5 nm or less in the (meth) acrylic polymer (P)
  • the values of MC ( ⁇ ) and MP ( ⁇ ) are almost the same. . If the phosphorus-based flame retardant (C) is dispersed in a domain having a size larger than that, the difference between the values of MC ( ⁇ ) and MP ( ⁇ ) increases.
  • the phosphorus flame retardant (C) When the content is 6% or less, the phosphorus flame retardant (C) is uniformly dissolved or finely dispersed without being localized, and the flame retardant improvement effect of the phosphorus flame retardant (C) is remarkably exhibited.
  • the present inventors have found that the effect that the flame retardancy of the (meth) acrylic resin composition is remarkably excellent is exhibited.
  • the above-mentioned (meth) acrylic resin composition is obtained by simply using a method for producing a (meth) acrylic resin composition, which will be described later, to convert a phosphorus flame retardant (C) into a (meth) acrylic polymer as a flame retardant.
  • a phosphorus flame retardant (C) into a (meth) acrylic polymer as a flame retardant.
  • the phosphorus-based flame retardant (C) is uniformly dissolved or finely dispersed without being localized, so that the flame retardant functions uniformly during combustion. It is considered that a phenomenon that the flame retardancy is remarkably improved has occurred.
  • the (meth) acrylic resin composition in order to increase the impact resistance of the resin molded body, has a multi-structure acrylic copolymer particle (D1), which will be described later, as an impact resistance improver (D) or will be described later. At least one compound selected from the acrylic block copolymer (D2) can be included as one of the constituent components.
  • the impact resistance improver (D) is 2.0 parts by mass or more and 50.0 parts per 100 parts by mass of the (meth) acrylic polymer (P). It can contain below mass parts.
  • the lower limit of the content of the impact resistance improver (D) with respect to 100 parts by mass of the (meth) acrylic polymer is preferably 2.0 parts by mass or more, since the impact resistance of the resin molded article becomes good, and preferably 5.0 More than mass part is more preferable.
  • the upper limit of the content of the impact resistance improver (D) with respect to 100 parts by mass of the (meth) acrylic polymer is 50.0 parts by mass or less, the flame retardancy and weather resistance of the resin molded product will be good. It is preferably 30.0 parts by mass or less, more preferably 20.0 parts by mass or less.
  • the multi-structure acrylic copolymer particles (D1) used in the present invention include elastomer particles (d1-1) comprising at least one rubbery copolymer layer having a crosslinked structure. As long as it has a rubbery copolymer layer having a crosslinked structure, the composition and particle diameter of each layer of the multi-structure acrylic copolymer particles (D1) are not limited.
  • multi-structure acrylic copolymer particles (D1-1) having a structure in which a hard resin layer (d1-2) is formed outside the elastomer particles (d1-1) can be given.
  • multi-structure acrylic copolymer particles (D1-2) in which a hard resin layer (d1-3) having a crosslinked structure is formed inside the elastomer particles (d1-1).
  • multi-structure acrylic copolymer particles in which a hard resin layer (d1-4) is further formed inside the hard resin layer (d1-2) and outside the hard resin layer (d1-2) (D1-3).
  • Multi-structured acrylic copolymer particles (D1-1) As the multi-structure acrylic copolymer particles (D1-1), a hard resin component is graft-polymerized on the surface of the elastomer particles (d1-1) made of a rubbery copolymer having a cross-linked structure, thereby obtaining a hard resin.
  • the multi-structure acrylic copolymer particles (D1-1) in which the layer (d1-2) is formed can be used.
  • Examples of the rubber-like copolymer constituting the elastomer particles (d1-1) include (co) polymers whose main component is a repeating unit derived from an alkyl acrylate ester.
  • the alkyl acrylate-derived repeating unit having an alkyl group having 1 to 8 carbon atoms is 70 to 90% by mass
  • the repeating unit derived from an aromatic vinyl monomer is 10 to 30% by mass
  • other copolymerizable components It is a (co) polymer containing 0 to 20% by mass of repeating units derived from monomers.
  • alkyl acrylate having 1 to 8 carbon atoms in the alkyl group examples include methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. These monomers are used alone or in combination of two or more.
  • aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, vinyltoluene and the like. These monomers are used alone or in combination of two or more.
  • Examples of the other copolymerizable monomers include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate, and vinyl cyanide compounds such as (meth) acrylonitrile.
  • the following polyfunctional monomer can also be included.
  • polyfunctional monomer examples include ethylene glycol di (meth) acrylate, 1,3-butylene di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, allyl (meth) acrylate, Examples thereof include a crosslinking agent such as divinylbenzene, and a crosslinking agent such as trimethylolpropane triacrylate, triallyl isocyanurate, and pentaerythritol tetraacrylate. These monomers are used alone or in combination of two or more.
  • the mass average particle diameter of the elastomer particles (d1-1) is not particularly limited, but is generally 100 to 300 nm.
  • the hard resin component that forms the hard resin layer (d1-2) can include a (co) polymer mainly composed of a repeating unit derived from a methacrylic acid ester. Specifically, the repeating unit derived from alkyl methacrylate having 1 to 4 carbon atoms in the alkyl group is 50% by mass or more and 100% by mass or less, and the repeating unit derived from alkyl acrylate having 1 to 8 carbon atoms in the alkyl group is 0% by mass or more. It is a (co) polymer containing 50% by mass or less and 0% by mass or more and 20% by mass or less of repeating units derived from other copolymerizable monomers.
  • alkyl methacrylate having 1 to 4 carbon atoms in the alkyl group examples include methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate and n-butyl methacrylate, and acrylic esters such as methyl acrylate and ethyl acrylate. It is done. These monomers are used alone or in combination of two or more.
  • Examples of the repeating unit derived from an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group derived from 0 to 50% by mass include an example in which elastomer particles (d1-1) containing a rubbery copolymer having the above-mentioned crosslinked structure are used. Similar ones can be used.
  • copolymerizable monomers include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene and vinyltoluene, nonalkyl methacrylates such as phenyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate, and the corresponding non-alkyl methacrylates. Examples thereof include alkyl acrylate.
  • the polyfunctional monomer mentioned above can also be included.
  • the multi-structure acrylic copolymer particle (D1) used in the present invention is a multi-structure acrylic copolymer particle in which a hard resin layer (d1-3) having a crosslinked structure is formed inside the elastomer particle (d1-1).
  • Polymer particles (D1-2) can be used.
  • Hard resin layer having a crosslinked structure examples include (co) polymers whose main component is a repeating unit derived from an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms.
  • the hard resin component forming the hard resin layer (d1-3) may be the same resin component as the hard resin layer (d1-2) or a different resin component.
  • the repeating unit derived from alkyl methacrylate having 1 to 4 carbon atoms in the alkyl group is 40% by mass or more and 100% by mass or less
  • the repeating unit derived from alkyl acrylate having 1 to 8 carbon atoms in the alkyl group is 0% by mass or more. 60% by mass or less, and 0% by mass to 20% by mass of repeating units derived from other copolymerizable monomers and 0.1% by mass to 10% by mass of repeating units derived from polyfunctional monomers ( And (co) polymers.
  • the monomer and the polyfunctional monomer those similar to the hard resin layer (d1-2) mentioned above can be used.
  • the hard resin layer (d1-3) when the elastomer particles (d1-1) are 100 parts by mass is not particularly limited, but generally 30 parts by mass or more and 100 parts by mass or less. .
  • Multi-structure acrylic copolymer particles (D1-3) are outside the hard resin layer (d1-2) of the multi-structure acrylic copolymer particles (D1-1) or (D1-2) described above. Furthermore, multi-structure acrylic copolymer particles (D1-3) in which a hard resin layer (d1-4) is further formed can be used.
  • Hard resin layer d1-4
  • examples of the hard resin component forming the hard resin layer (d1-4) include (co) polymers mainly composed of repeating units derived from methyl methacrylate.
  • Tg glass transition temperature
  • multi-structure acrylic copolymer particles (D1) described above can be produced by a known method.
  • the lower limit of the content of the multi-structure acrylic copolymer particles (D1) in the (meth) acrylic resin composition is from the viewpoint of improving the impact resistance of the resin molded product.
  • (P) 2.0 mass parts or more are preferable with respect to 100 mass parts, and 5.0 mass parts or more are more preferable.
  • the upper limit of the content of the multi-structure acrylic copolymer particles (D1) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, from the viewpoint of maintaining good flame retardancy and weather resistance of the resin molded product. .
  • the acrylic block copolymer (D2) used in the present invention comprises an acrylic block copolymer having a methacrylic acid ester polymer block (d2-1) and an acrylic acid ester polymer block (d2-2). Specifically, an acrylic block having a methacrylic acid ester polymer block (d2-1) of 10% by mass to 60% by mass and an acrylic ester polymer block (d2-1) of 40% by mass to 90% by mass. Mention may be made of copolymers. Further, when the acrylate polymer block (d2-2) comprises an acrylate alkyl ester and a (meth) acrylate aromatic ester, the acrylate polymer block (d2-2) is an acrylate alkyl ester. It is preferable to contain 50 to 90% by mass of structural units derived from the above and 50 to 10% by mass of structural units derived from the (meth) acrylic acid aromatic ester.
  • acrylic block copolymer (D2) other than the above for example, a commercially available product such as “Clarity” manufactured by Kuraray Co., Ltd. can be obtained.
  • the lower limit of the content of the acrylic block copolymer (D2) in the (meth) acrylic resin composition is that the (meth) acrylic polymer (P ) 2.0 mass parts or more is preferable with respect to 100 mass parts, and 5.0 mass parts or more is more preferable.
  • the upper limit of the content of the acrylic block copolymer (D2) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, from the viewpoint of favorably maintaining the flame retardancy and weather resistance of the resin molding. More preferred is less than or equal to parts by weight.
  • Examples of a method for obtaining the (meth) acrylic resin composition of the present invention include a method of polymerizing a polymerizable composition (X3) described later.
  • Examples of the radical polymerization initiator used when polymerizing the polymerizable composition (X3) to obtain a (meth) acrylic resin composition include 2,2′-azobis (isobutyronitrile), 2 Azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile) and peroxides such as benzoyl peroxide and lauroyl peroxide. If necessary, accelerators such as amines and mercaptans can be used in combination with the radical polymerization initiator.
  • the polymerization temperature for polymerizing the polymerizable composition (X3) is usually appropriately set in the range of 20 to 150 ° C. depending on the type of radical polymerization initiator used. Further, the polymerizable composition (X3) can be polymerized under a multi-stage temperature condition as necessary.
  • Examples of the polymerization method of the polymerizable composition (X3) include a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a dispersion polymerization method.
  • the bulk polymerization method is used in terms of productivity.
  • cast polymerization cast polymerization is more preferable.
  • the (meth) acrylic resin composition can be obtained by injecting the polymerizable composition (X3) into a mold and polymerizing the composition.
  • a material in which a sealing material such as a soft vinyl chloride resin tube is sandwiched between the end portions of the SUS plate in the space between the two SUS plates can be used.
  • the space between the mold gaps is appropriately adjusted so as to obtain a resin plate having a desired thickness, but is generally 1 to 30 mm.
  • the polymerizable composition (X3) is an embodiment of a raw material for obtaining a (meth) acrylic resin composition.
  • the monomer composition (X1), the phosphorus flame retardant (C), and the It is a composition containing an amphiphilic compound (E).
  • the monomer composition (X1) can include a polymer containing a repeating unit derived from (meth) acrylic acid ester in advance.
  • the monomer composition (X1) can include in advance a polymer (P1) containing a repeating unit derived from the (meth) acrylic acid ester (M).
  • P1 polymer containing a repeating unit derived from the (meth) acrylic acid ester (M).
  • the polymerizable composition (X3) becomes a viscous liquid (hereinafter referred to as “syrup”), so that the polymerization time can be shortened and the productivity can be improved.
  • a method for obtaining the syrup described above for example, a method in which a polymer is dissolved in the monomer composition (X1), or a known radical polymerization initiator is added to the monomer composition (X1). And a method of polymerizing the parts.
  • the polymerizable composition (X3) comprises the monomer composition (X1), the amphiphilic compound (E), and, if necessary, the polymer (P1).
  • the phosphorus flame retardant (C) is preferably added later to the mixture (X2) contained in advance. Further, when it contains at least one kind of impact resistance improver (D) selected from the multi-structure acrylic copolymer particles (D1) or the acrylic block copolymer (D2), the impact resistance improver ( It is preferable to add D) to the mixture (X2) and further add the phosphorus-based flame retardant (C) later to obtain the polymerizable composition (X3).
  • a (meth) acrylic resin composition having high flame retardancy can be stably produced.
  • the reason is not clear, but when the phosphorus-based flame retardant (C) is added to the monomer composition (X1) in the absence of the amphiphilic compound (E), the phosphorus-based flame retardant forms aggregated particles. Inferred to form.
  • the polymerizable composition (X3) includes the monomer composition (X1) as 100 parts by mass, the phosphorus-based flame retardant (C) being 5.0 parts by mass or more and 35.0 parts by mass or less, Amphiphilic compound (E) can be contained in an amount of 0.01 to 2.0 parts by mass.
  • the polymerizable composition (X3) is a syrup containing a polymer
  • the total amount of the monomer composition (X1) and the polymer may be 100 parts by mass. If the minimum of content of a phosphorus flame retardant (C) is 5.0 mass parts or more, the flame retardance of a resin molding will become favorable. Moreover, if the upper limit of content of a phosphorus flame retardant (C) is 35.0 mass parts or less, the heat resistance of a resin molding will become favorable.
  • the phosphorus-based flame retardant (C) does not form aggregated particles, and the flame retardancy of the resin molded body is improved.
  • 0.05 mass part or more is more preferable, and 0.1 mass part or more is still more preferable.
  • the upper limit of the content of the amphiphilic compound (E) is 2.0 parts by mass or less, the flame retardancy of the resin molded article becomes good, preferably 0.6 parts by mass or less, more preferably 0.3 More preferred is less than or equal to parts by weight.
  • the contents of the (meth) acrylic acid ester (M), methyl methacrylate and monomer (B) of the polymerizable composition (X3) are not particularly limited, and for example, a (meth) acrylic resin
  • the (meth) acrylic polymer (P) contained in the composition has a repeating unit derived from methyl methacrylate of 19.95% by mass to 84.95% by mass and a (meth) acrylic acid ester (based on the total mass). It is determined as appropriate so that it contains 3.6% by mass or more and 80.0% by mass or less of the repeating unit derived from M) and 0.05% by mass or more and 0.40% by mass or less of the structural unit derived from the monomer (B). it can.
  • polymerizable composition (X3) when the polymerizable composition (X3) is syrup, a composition containing the following polymer (a) and monomer composition (X1) is mentioned. It is done.
  • Monomer composition (X1) Methyl methacrylate 19.95 mass% or more, (meth) acrylic acid ester (M) monomer 3.6 mass% or more with respect to the total mass of monomer composition (X1)
  • the polymerizable composition (X3) obtained by the method described above can have a longer pot life than the polymerizable composition obtained by the conventional method. Specifically, since the pot life can be set to about 168 hours, there is an effect of facilitating production management at the manufacturing site.
  • the temperature at which the polymerizable composition is stored is not particularly limited.
  • the lower limit of the storage temperature is preferably 5 ° C. or more, because there are few restrictions on equipment, and preferably 10 ° C. or more. More preferred.
  • the upper limit of the storage temperature is not particularly limited, but if it is 40 ° C. or less, it is preferable from the viewpoint of storage safety, and 30 ° C. or less is more preferable.
  • the monomer composition (X1) is a composition containing the (meth) acrylic acid ester (M). By including the (meth) acrylic acid ester (M), the flame retardancy of the resin molded body is improved, and the phosphorus-based flame retardant (C) is agglomerated by the action of the amphiphilic substance (E) described above. It can suppress forming. Furthermore, when the monomer composition (X1) contains the (meth) acrylic acid ester (M), it can contain methyl methacrylate and the monomer (B). By containing methyl methacrylate, the resin molded article is excellent in heat resistance and weather resistance, and more excellent in mechanical strength, thermal properties, and moldability.
  • (meth) acrylic acid ester (M), methyl methacrylate, and monomer (B) in monomer composition (X1) is not specifically limited,
  • the (meth) acrylic polymer (P) contained in the composition has a repeating unit derived from methyl methacrylate of 19.95% by mass to 84.95% by mass and a (meth) acrylic acid ester (based on the total mass). It is determined as appropriate so that it contains 3.6% by mass or more and 80.0% by mass or less of the repeating unit derived from M) and 0.05% by mass or more and 0.40% by mass or less of the structural unit derived from the monomer (B). it can.
  • the (meth) acrylic acid ester (M) has an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain.
  • Ester (M2) 0.50 with ester (M1) 10.0 mass% or more and 79.5 mass% or less and an aromatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the side chain Mass% or more and 20.0 mass% or less.
  • the methacrylic acid ester (M1) and the acrylic acid ester (M2) interact with the phosphorus flame retardant (C) and have the effect of synergistically increasing the flame retardant improvement effect of the phosphorus flame retardant (C). Therefore, the flame retardance of the resin molding can be improved.
  • the weather resistance of the obtained resin molding becomes favorable.
  • the methacrylic acid ester (M1) and the acrylic acid ester (M2) include the compounds described above.
  • the methacrylic acid ester (M1) may be at least one selected from cyclohexyl methacrylate and isobornyl methacrylate from the viewpoint of excellent flame retardancy and flame resistance.
  • the (meth) acrylic acid ester (M2) is at least one selected from cyclohexyl acrylate and isobornyl acrylate (hereinafter referred to as “monomer (m2)”) from the viewpoint of excellent effects of improving flame retardancy and weather resistance. ),
  • the weather resistance and flame retardancy of resin molding can be improved.
  • Content of a monomer (m2) can be 1.0 mass part or more and 4.99 mass parts or less.
  • polymerization can be reduced more, and the weather resistance of resin molding becomes more favorable.
  • the monomer (m2) interacts with the phosphorus flame retardant and has the effect of synergistically enhancing the flame retardant improvement effect of the phosphorus flame retardant, thus improving the flame retardancy of the resin molded body. it can.
  • the minimum of content of a monomer (m2) is not specifically limited, By setting it as 1.0 mass% or more with respect to 100 mass parts of said (meth) acrylic-type polymers (P). From the viewpoint that the flame retardancy and weather resistance of the resin molded body can be improved, 2.0% by mass or more is more preferable.
  • the upper limit of the content is not particularly limited, but if the content is 4.99% by mass or less, it is preferable because the heat resistance of the resin molded body can be further improved, and 4.0% by mass or less is more preferable. preferable.
  • the above upper limit value and lower limit value can be arbitrarily combined.
  • a polymer (P1) further containing a repeating unit derived from the (meth) acrylic acid ester (M) in the monomer composition (X1) or examples thereof include those obtained by partially polymerizing the monomer composition (X1), such as those in the form of a viscous liquid (hereinafter referred to as “syrup”).
  • the monomer composition (X1) for example, when the polymerizable composition (X3) is a monomer composition (X1) consisting only of monomers, the monomer composition ( X1) with respect to the total mass of methyl methacrylate 19.95 mass% or more and 84.95 mass% or less, (meth) acrylic ester (M) monomer 15.0 mass% or more and 80.0 mass% or less And a composition containing 0.05% by mass or more and 0.40% by mass or less of the monomer (B).
  • methyl methacrylate is 19.95 mass% or more and 79.1 mass% or less with respect to the total mass of the monomer composition (X1).
  • the monomer composition (X1) contains 0.05% by mass or more and 0.40% by mass or less of the monomer (B) having two or more ethylenically unsaturated bonds in the molecule.
  • the manufacturing method of a (meth) acrylic-type resin composition is mentioned.
  • ⁇ Production method of resin molding> the manufacturing method of a resin molding is not specifically limited, For example, the following two methods are mentioned. (1) A method in which the polymerizable composition (X3) is poured into a mold and polymerized using a known cast polymerization method, and then taken out from the mold to obtain a resin molded body. (2) A method of obtaining a resin molded product from the (meth) acrylic resin composition pellets of the present invention using a known melt molding method such as extrusion molding or injection molding.
  • the resin laminate of the present invention is a sheet-like resin laminate in which the above-mentioned resin molded body is used as the resin base material (A) and a cured film (F) described later is provided on at least one surface thereof.
  • the resin base material (A) is a layer for imparting high flame retardancy, heat resistance and weather resistance to the resin laminate, and the cured coating (F) is for imparting high scratch resistance to the resin laminate. Layer.
  • FIG. 2 is a schematic view of a resin laminate having a cured coating (F) on one surface of the resin substrate (A).
  • FIG. 3 is a schematic view of a resin laminate having a cured coating (F) on both surfaces of the resin substrate (A).
  • the cured film (F) is a polyfunctional monomer (F1) having three or more (meth) acryloyl groups described later (hereinafter referred to as “polyfunctional monomer (F1)”). And a polyfunctional monomer (F2) having two (meth) acryloyl groups described later (hereinafter abbreviated as “polyfunctional monomer (F2)”). It is a cured film made of a cured product of the curable composition (f) (hereinafter referred to as “curable composition (f)”).
  • the content of the repeating unit derived from the polyfunctional monomer (F1) and the repeating unit derived from the polyfunctional monomer (F2) contained in the cured film (F) is particularly Although not limited, the total weight of the cured coating (F) is 100% by mass, and the repeating unit derived from the polyfunctional monomer (F1) is 50% by mass to 80% by mass and the polyfunctional monomer (F2). It can be set as the resin composition containing 20 mass% or more and 50 mass% of derived repeating units.
  • the lower limit of the content of the repeating unit derived from the polyfunctional monomer (F1) is preferably 50% by mass or more, and more preferably 60% by mass or more because the scratch resistance of the cured film (F) is improved.
  • the upper limit of the content of the repeating unit derived from the polyfunctional monomer (F1) is that the cured coating film (F) has a small curing shrinkage rate and is less prone to cracking, and a laminated resin plate on which the cured coating film (F) is formed. Therefore, 80% by mass or less is preferable, and 70% by mass or less is more preferable.
  • the above upper limit value and lower limit value can be arbitrarily combined.
  • the upper limit of the content of the repeating unit derived from the polyfunctional monomer (F2) is preferably 50% by mass or less, and more preferably 40% by mass or less because the scratch resistance of the cured film is improved.
  • the lower limit of the content of the repeating unit derived from the polyfunctional monomer (F2) is that the curing shrinkage rate when the composition is cured is small, cracks are less likely to occur in the cured coating (F), and the resin substrate (A ) And the cured coating film (F), the content is preferably 20% by mass or more, and more preferably 30% by mass or more.
  • the above upper limit value and lower limit value can be arbitrarily combined.
  • a resin laminate having high scratch resistance can be obtained by containing a repeating unit derived from the polyfunctional monomer (F1) in the cured coating (F).
  • polyfunctional monomer (F1) examples include the following (1) to (5). These may be used alone or in combination of two or more.
  • malonic acid / trimethylolethane / (meth) acrylic acid malonic acid / trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (meta )
  • Acrylic acid succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meth)
  • Known compounds such as acrylic acid can be mentioned.
  • polyisocyanate obtained by trimerization examples include known compounds such as trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, and tolylene diisocyanate.
  • acrylic monomer having active hydrogen examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, And known compounds.
  • poly [(meth) acryloyloxyethylene] isocyanurate examples include di (meth) acrylate or tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid.
  • pentaerythritol tri (meth) acrylate tris ((meth) acryloxyethyl) isocyanurate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, penta described in (1) above.
  • polyfunctional monomer (F2) examples include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate.
  • 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate are more preferable because they are excellent in adhesion to the substrate of the cured film and scratch resistance.
  • the cured film (F) can be obtained by curing the curable composition (f) containing the polyfunctional monomer (F1) and the polyfunctional monomer (F2) by a known method. .
  • the curable composition (f) contains 50% by mass to 80% by mass of the polyfunctional monomer (F1) and 20% by mass to 50% by mass of the polyfunctional monomer (F2).
  • a curable composition obtained by adding a predetermined amount of a photopolymerization initiator described later to the curable composition (f) as necessary can be used.
  • the upper limit of the content of the polyfunctional monomer (F1) is that the cured shrinkage rate of the cured film (F) decreases, cracks are less likely to occur, and the laminated resin plate on which the cured film (F) is formed is warped. Since there exists a tendency which it becomes difficult to produce, 80 mass% or less is preferable and 70 mass% or less is more preferable.
  • the lower limit of the content of the polyfunctional monomer (F1) is preferably 50% by mass or more, and more preferably 60% by mass or more because the scratch resistance of the cured film (F) is improved. The above upper limit value and lower limit value can be arbitrarily combined.
  • the upper limit of the content of the polyfunctional monomer (F2) is preferably 50% by mass or less, and more preferably 40% by mass or less because the scratch resistance of the cured film becomes good.
  • the lower limit of the content of the polyfunctional monomer (F1) is preferably 20% by mass or more because the curing shrinkage rate when curing the curable composition is small and cracks are hardly generated in the cured film (F). 30% by mass or more is more preferable.
  • the above upper limit value and lower limit value can be arbitrarily combined.
  • Photopolymerization initiator A known compound can be used as the photopolymerization initiator. Specifically, benzoin and its derivatives, benzopheno and its derivatives, acetophenone and its derivatives, carbonyl compounds such as alkylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, tetramethylthiuram And sulfur compounds such as monosulfide. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.
  • the addition amount of the photopolymerization initiator is not particularly limited, but 0.5 parts by mass or more and 6.0 parts by mass or less of the photopolymerization initiator is added to 100 parts by mass of the curable composition (f). be able to.
  • ⁇ Other additives Various additives conventionally used can be added to the curable composition (f) as necessary. Specific examples include surfactants, leveling agents, dyes, pigments, antioxidants, UV absorbers, stabilizers, flame retardants, plasticizers, and monofunctional monomers for imparting functions. .
  • the addition amount of an additive is suitably determined within the range in which the physical property of the obtained cured film (F) is not impaired, it should be 10 parts by mass or less with respect to 100 parts by mass of the curable composition (f). Can do.
  • ⁇ Thickness of resin laminate> The total thickness of the resin laminate of the present invention is not particularly limited, but is preferably 1 mm or more and 30 mm or less, and more preferably 3 mm or more and 10 mm or less because the resin laminate is excellent in moldability and flame retardancy.
  • the total thickness of the resin laminate means the sum of the thickness of the resin base material (A) and the thickness of the cured coating (F).
  • the thickness of the cured film (F) of the resin laminate of the present invention is not particularly limited, but is preferably 0.1 ⁇ m or more and 100 ⁇ m or less because the resin laminate is excellent in scratch resistance and flame retardancy. 3 ⁇ m or more and 30 ⁇ m or less is more preferable.
  • the manufacturing method of a resin laminated body is not specifically limited, The manufacturing method of the well-known resin laminated body performed by a batch type or a continuous type can be used.
  • a sheet-like resin base material (A) is manufactured by a known continuous casting method, and then continuously on at least one surface of the resin base material (A) in-line. And a method of producing a resin laminate by laminating the above-described cured coating (F).
  • the continuous casting method is preferable because the productivity of the resin laminate is excellent.
  • Method (1) A layer of the curable composition (f) composed of the polyfunctional monomer (F1) and the polyfunctional monomer (F2) was formed on at least one surface of the resin base material (A). Then, it hardens
  • Method (2) The curable composition (f) comprising the polyfunctional monomer (F1) and the polyfunctional monomer (F2) is cured to form a cured film (F), and then the curing is performed.
  • a method of obtaining a resin laminate by forming a layer of a resin substrate (A) on the surface of a coating (F).
  • the polymerizable composition (X3) is injected as a raw material for the resin base material (A) into a mold, and the polymerizable composition (X3) is cured by cast polymerization and peeled off from the mold.
  • a resin base material (A) is obtained.
  • the curable composition (f) containing the polyfunctional monomer (F1) and the polyfunctional monomer (F2) is applied to the surface of the resin base material (A), and the surface is covered with a resin film.
  • the curable composition (f) is cured by irradiating the curable composition (f) with an active energy ray through a resin film to obtain a cured film (F). Thereafter, the resin film is peeled off to obtain a resin laminate.
  • mold types include molds such as molds and sheets.
  • the mold is usually prepared by placing two molds facing each other so that the surface on which the cured film is formed is on the inside.
  • the surface on which the cured film is formed in the mold preferably has a smooth surface.
  • the mold material include stainless steel, glass, and resin.
  • the mold may be a mold in which two molds of the same material are opposed to each other, or a mold in which two molds of different materials are opposed to each other.
  • a laminated mold having a certain volume on the inside is produced by providing a gasket at the peripheral edge of a space formed between the molds and sealing.
  • the resin film examples include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, and a polyvinylidene fluoride (PVDF) film.
  • PET polyethylene terephthalate
  • PP polypropylene
  • PE polyethylene
  • PVDF polyvinylidene fluoride
  • the thickness of the resin film is preferably 8 to 125 ⁇ m.
  • Examples of the active energy rays include electron beams, ultraviolet rays, and visible rays, but ultraviolet rays are preferable from the viewpoints of apparatus cost and productivity.
  • the light amount of the active energy ray is not particularly limited, but an integrated light amount of 5 to 2000 mJ / cm 2 is preferable.
  • the resin base material (A) After using the pellets of the (meth) acrylic resin composition to obtain a sheet-like resin base material (A) by a melt molding method such as extrusion molding or injection molding, the resin base material (A) The method of forming the layer of a cured film (F) on the surface of this using the well-known dapping method is mentioned.
  • the batch production method (2) include the following methods. First, the curable composition (f) containing the polyfunctional monomer (F1) and the polyfunctional monomer (F2) is applied to the inner surface of the mold, and the surface is covered with a resin film. Next, the curable composition (f) is cured by irradiating the curable composition (f) with an active energy ray through a resin film to obtain a cured coating film (F). Thereafter, the resin film is peeled off to obtain a laminated mold in which the cured film (F) is laminated on the inner surface of the mold.
  • a cured film (F ) Is laminated to obtain a resin substrate (A). Then, it peels from a casting_mold
  • a template similar to the above-described template can be used.
  • the resin film a film similar to the resin film described above can be used.
  • the active energy rays the same energy rays as the above-mentioned active energy rays can be used, and the curing method using the active energy rays can be cured by the same method as described above.
  • MMA Methyl methacrylate
  • IBXMA Isobornyl methacrylate
  • IBXA Isobornyl acrylate
  • TBMA t-butyl methacrylate
  • EDMA ethylene glycol dimethacrylate
  • CR-570 halogen-containing condensed phosphate ester (trade name, large (Manufactured by Hachi Chemical Industry Co., Ltd.)
  • CR-504L Halogen-containing condensed phosphate ester (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.)
  • SDS sodium dioctyl sulfosuccinate SS: sodium stearate
  • SLS sodium lauryl sulfate
  • PEH 2-ethylhexyl phosphate
  • HPP t-hexyl peroxypivalate
  • CHMA cyclohexyl methacrylate
  • JIS Flame resistance
  • Dispersion Particle Diameter The resin molded body or (meth) acrylic resin composition is observed at a magnification of 1000 times using an optical microscope, and the observed dispersed particles or aggregated particles 20 of any phosphorus-based flame retardant (C). For each particle, the primary particle size of the dispersed particles or the secondary particle size of the aggregated particles was measured, and the average value was taken as the dispersed particle size. When no dispersed particles were observed, “ND” was set. The secondary particles formed by contacting the dispersed particles (primary particles) were used as aggregated particles.
  • the peak width at the half of the height from the peak baseline to the peak top was defined as the half width of the peak. Even when the peak shape is not a normal distribution, the half width is obtained by the above method.
  • the most characteristic mass-to-charge ratio (m / z) of the generated gas of (meth) acrylic acid ester (M) and the decomposition product of phosphorus flame retardant (C) should be measured with a single sample. You can find out at The mass-to-charge ratio (m / z) of the compounds used in the examples and comparative examples is shown below.
  • the temperature Tm (° C.), the generation temperature Ta (° C.) of the decomposition product of the repeating unit derived from methyl methacrylate, and the generation temperature Tc (° C.) of the decomposition product of the phosphorus flame retardant (C) were measured.
  • the peak observed when the chromatogram is drawn at the mass-to-charge ratio (m / z), which is the most characteristic as a decomposition product generation gas of (meth) acrylate (M), is )
  • the peak of the generated gas of the decomposition product of the repeating unit derived from the acrylate ester (M) and the peak observed when the chromatogram was drawn at the characteristic mass number as the generated gas of methyl methacrylate are derived from methyl methacrylate.
  • the peak of the generated gas of the decomposition product of the repeating unit of the above and the peak observed when the chromatogram was drawn at the characteristic mass number as the decomposition product generating gas of the phosphorus-based flame retardant (C) are the phosphorus-based flame retardant
  • the peak of the generated gas of the decomposition product of (C) the highest point of the peak of the temperature-chromatogram curve was taken as the generation temperature of the decomposition product
  • the sample is used for measurement by cutting 2 mg from the resin composition. At this time, the decomposition characteristics may change depending on the size of the sample.
  • Charpy impact strength The notched Charpy impact strength was measured according to JIS K7111-1 / fU.
  • a guard column (trade name: TSK-guardcolumn SUPERH-L, manufactured by Tosoh Corporation) was connected to a high performance liquid chromatography measuring apparatus (manufactured by Tosoh Corporation, apparatus name: HLC-8320 type).
  • a separation column (product name: SUPER H2000, 6.0 mm ⁇ ⁇ 150 mm, manufactured by Tosoh Corporation) is connected to a separation column (product names: SUPER H4000, 6.0 mm ⁇ ⁇ 150 mm, manufactured by Tosoh Corporation).
  • a differential refractometer was used as the detector.
  • the measurement was performed with a separation column temperature of 40 ° C., THF as the moving bed, a flow rate of the moving bed of 0.6 ml / min, and a sample injection amount of 10 ⁇ l.
  • Calibration curves using 10 polystyrenes with known molecular weights (Mw 5,970, ⁇ 6,770,000), Irganox 1010 (Mw1178) and 2,2'-methylenebis (6-tert-butyl-p-cresol) (Mw340) (Tertiary formula) was prepared, and the weight average molecular weight (Mw) was determined.
  • Solid-state NMR measurement apparatus AVANCE II 300 (Bruker Biospin) ⁇ Measurement temperature: Room temperature (22 °C) -Observation nucleus: 13 C (observation frequency: 75.4 MHz) 31 P (observation frequency is 121 MHz) ⁇ Contact time: 2000 ⁇ s ⁇ Pulse sequence: described in FIG. 1 ⁇ Sample rotation speed: 6 kHz ⁇ Repetition time: 4 sec ⁇ Number of integration: 512 times ⁇ Spinlock time: 16, 20, 25, 30 msec The reference of the 13 C nuclear spectrum was that the carbonyl peak of glycine was 176.03 ppm. In the 31 P nuclear spectrum, the highest intensity peak was set to 0 ppm.
  • the 13 C nuclear spectrum and 31 P nuclear spectrum were measured by a spin lock cross polarization method (CP method) at a predetermined spin lock time ⁇ (unit: msec).
  • the spectrum (peak) corresponding to carbon of the carbonyl group of the acrylic resin composition is -180 ppm to -160 ppm of the 13 C nucleus spectrum, and the spectrum (peak) corresponding to the phosphorus atom of the phosphorus flame retardant (C) is 31 P nucleus.
  • the following MC ( ⁇ ) and MP ( ⁇ ) were measured at ⁇ 40 to 40 ppm of the spectrum, and the value D 1 (%) was calculated from the following formula (a).
  • D 1 (%)
  • Example 1 Manufacture of syrup (A1) In a reactor (polymerization kettle) equipped with a cooling pipe, a thermometer and a stirrer, a single amount comprising 68 parts by mass of MMA, 20 parts by mass of IBXMA, 3 parts by mass of IBXA, 8 parts by mass of TBMA, and 1 part by mass of BA Body composition was charged. The monomer composition was stirred at a room temperature while bubbling with nitrogen gas, and then heated to a temperature of 60 ° C. while stirring.
  • CR-570 as a phosphorus-based flame retardant (C)
  • t-hexylperoxypivalate as a polymerization initiator
  • a mold was prepared by installing a vinyl chloride resin gasket at the peripheral edge between two SUS plates arranged to face each other so that the gap between the two SUS plates was 4.1 mm. After adjusting the polymerizable composition (X3) and allowing to stand for 1 hour, after pouring the polymerizable composition (X3) into the mold and completely sealing with a vinyl chloride resin gasket, The temperature was immediately raised to 82 ° C.
  • the flame retardancy of the resin molding was 1.0 minutes in the self-extinguishing time in the flame resistance test method A of JIS K 6911-1995 (hereinafter abbreviated as “flame retardance (JIS)”). Moreover, when the obtained resin molding was observed using the optical microscope, the aggregated particle exceeding 0.1 micrometer was not observed. The value D 1 is 2.7%, the value D 2 was 5.1%.
  • Example 2 and 3 A resin molded body was obtained in the same manner as in Example 1 except that the time from the addition of CR-570 as the phosphorus-based flame retardant (C) to the start of polymerization was changed as shown in Table 2. .
  • Table 4 shows the evaluation results of the obtained resin molding.
  • Example 4 Except that the addition amount of the phosphorus-based flame retardant (C) and the time from the addition of CR-570 as the phosphorus-based flame retardant (C) to the start of polymerization were changed as shown in Table 2, the examples 1 to obtain a resin molded body. Table 4 shows the evaluation results of the obtained resin molding.
  • Example 7 and 8 A resin molded body was obtained in the same manner as in Example 1 except that the amount of the amphiphilic compound (E) added was changed as shown in Tables 2 and 4. Table 4 shows the evaluation results of the obtained resin molding.
  • Example 9 Example except that 0.2 parts by mass of SS (sodium stearate) was added as the amphiphilic compound (E) and the addition amount of the phosphorus-based flame retardant (C) was changed as shown in Tables 2 and 4. 1 to obtain a resin molded body.
  • Table 4 shows the evaluation results of the obtained resin molding.
  • Example 11 and 12 Example 1 except that 0.2 part by mass of SLS (sodium lauryl sulfate) was added as the amphiphilic compound (E) and the addition amount of the phosphorus-based flame retardant (C) was changed as shown in Tables 2 and 4. In the same manner as above, a resin molded body was obtained. Table 4 shows the evaluation results of the obtained resin molding.
  • SLS sodium lauryl sulfate
  • Example 13 and 14 Polymerization is carried out after adding 0.05 parts by mass of PEH (2-ethylhexyl phosphate) as the amphiphilic compound (E), adding the amount of phosphorus-based flame retardant (C) and phosphorus-based flame retardant (C).
  • PEH 2-ethylhexyl phosphate
  • C phosphorus-based flame retardant
  • C phosphorus-based flame retardant
  • Example 15 A resin molded body was obtained in the same manner as in Example 1 except that CR-504L was used as the phosphorus-based flame retardant (C) and the addition amount was changed as shown in Tables 2 and 4. Table 4 shows the evaluation results of the obtained resin molding.
  • Comparative Example 2 A resin molded body was obtained in the same manner as in Comparative Example 1 except that the addition amount of the phosphorus-based flame retardant (C) was changed as shown in Tables 3 and 5. Table 5 shows the evaluation results of the obtained resin molded body.
  • syrup (A2) composed of 30% by mass of the polymer and 70% by mass of the monomer composition (breakdown is MMA 91% by mass, BA 1% by mass). It was.
  • SDS sodium dioctylsulfosuccinate
  • Comparative Example 6 A resin molded body was obtained in the same manner as in Comparative Example 5 except that the addition amount of the phosphorus-based flame retardant (C) was changed as shown in Tables 3 and 5. Table 5 shows the evaluation results of the obtained resin molded body.
  • Example 7 When the resin molded body obtained in Example 7 was observed with an optical microscope, particles of a phosphorus-based flame retardant (C) having a dispersed particle diameter of 0.8 ⁇ m were observed. However, flame retardancy (JIS) and heat resistance were observed. The property was good. In the resin molded product obtained in Example 8, no dispersed particles of the phosphorus-based flame retardant (C) were observed, and the flame retardancy (JIS) and heat resistance were good. When the resin molded body obtained in Example 9 was observed with an optical microscope, dispersed particles of the phosphorus-based flame retardant (C) were not observed, and the flame retardancy (JIS) and heat resistance were good.
  • C phosphorus-based flame retardant having a dispersed particle diameter of 0.8 ⁇ m were observed. However, flame retardancy (JIS) and heat resistance were observed. The property was good. In the resin molded product obtained in Example 8, no dispersed particles of the phosphorus-based flame retardant (C) were observed, and the flame retardancy
  • Example 10 When the resin molded product obtained in Example 10 was observed with an optical microscope, no dispersed particles of the phosphorus-based flame retardant (C) were observed, and the flame retardancy (JIS and UL94) and heat resistance were good. .
  • Example 11 When the resin molded body obtained in Example 11 was observed with an optical microscope, dispersed particles of the phosphorus-based flame retardant (C) were not observed, and the flame retardancy (JIS) and heat resistance were good.
  • the resin molded body obtained in Example 12 When the resin molded body obtained in Example 12 was observed with an optical microscope, no dispersed particles of the phosphorus-based flame retardant (C) were observed, and the flame retardancy (JIS and UL94) and heat resistance were good. .
  • Example 13 When the resin molded body obtained in Example 13 was observed with an optical microscope, no dispersed particles of the phosphorus-based flame retardant (C) were observed, and the flame retardancy (JIS) and heat resistance were good.
  • the resin molded body obtained in Example 14 was observed with an optical microscope, dispersed particles of the phosphorus-based flame retardant (C) were not observed, and the flame retardancy (JIS and UL94) and heat resistance were good.
  • Example 15 When the resin molded body obtained in Example 15 was observed with an optical microscope, no dispersed particles of the phosphorus-based flame retardant (C) were observed, and the flame retardancy (JIS) and heat resistance were good.
  • Example 16 (1) Production of syrup (A3) In a reactor (polymerization kettle) equipped with a cooling pipe, a thermometer and a stirrer, 70 parts by mass of MMA and 30 parts of IBXMA as (meth) acrylic acid ester (M) Was introduced. The monomer composition was stirred at a room temperature while bubbling with nitrogen gas, and then heated to a temperature of 60 ° C. while stirring. Next, 0.1 part by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) as a radical polymerization initiator is added to 100 parts by mass of the monomer composition, The composition was heated to 100 ° C. with stirring and then held for 13 minutes.
  • syrup (A3) composed of 30% by mass of the polymer and 70% by mass of the monomer composition (the breakdown was MMA 70% by mass, IBXMA 30% by mass). It was.
  • SDS sodium dioctylsulfosuccinate
  • CR-570 as a phosphorus-based flame retardant (C)
  • t-hexylperoxypivalate as a polymerization initiator
  • a mold was prepared by installing a vinyl chloride resin gasket at the peripheral edge between two SUS plates arranged to face each other so that the gap between the two SUS plates was 4.1 mm.
  • the polymerizable composition (X3) was prepared and allowed to stand for 168 hours, the polymerizable composition (X3) was poured into the mold and completely sealed with a vinyl chloride resin gasket. The temperature was raised to 82 ° C.
  • the temperature was raised to 130 ° C. and held for 30 minutes to polymerize the polymerizable composition (X3). That is, the time from the addition of the phosphorus flame retardant (C) to the start of polymerization was 168 hours. Subsequently, after cooling to room temperature, the SUS board was removed and the plate-shaped resin molding of thickness 3mm was obtained. 2 mg was cut from the obtained molded product, and the half-value width of the peak of the decomposition product and the generation temperature of the decomposition product were determined.
  • m / z100 was used as methyl methacrylate
  • m / z93 was used as a side chain detachment of (meth) acrylic acid ester (M)
  • m / z76 was used as a phosphorus flame retardant (C).
  • the cut surface of the test piece was polished with a milling machine. Table 7 shows the evaluation results of the resin molding.
  • the obtained resin molded body was flame retardant (JIS and UL94), had good flame retardancy, and had a heat resistance of 81 ° C.
  • Example 17 to 21 A resin molded product was obtained in the same manner as in Example 16 except that the type of (meth) acrylic acid ester (M) was as shown in Table 6. Table 7 shows the evaluation results of the resin molding.
  • the resin molded bodies of Examples 17 and 18 had good flame retardancy (JIS and UL94) and heat resistance.
  • the (meth) acrylic ester (M) decomposition product had a half width of more than 26 and (Ta-Tm) of less than 100, so that the flame retardancy (JIS) was low. It was a little low.
  • Example 22 As shown in Table 6, a resin molded product was obtained in the same manner as in Example 16 except that the type of (meth) acrylic acid ester (M) was a combined use of methacrylic acid ester (M1) and acrylic acid ester (M2). . Table 7 shows the evaluation results of the resin molding.
  • the resin molded body of Example 22 had good flame resistance (JIS and UL94) and heat resistance.
  • Example 23 and 24 A resin molded body was obtained in the same manner as in Example 15 except that the type and addition amount of the phosphorus flame retardant (C) were as shown in Table 6. Table 7 shows the evaluation results of the resin molding. The resin moldings of Examples 23 and 24 were excellent in flame retardancy (JIS) and heat resistance.
  • JIS flame retardancy
  • Example 25 A resin molded body was obtained in the same manner as in Example 16 except that the addition amount of (meth) acrylic acid ester (M) was as shown in Table 6. Table 7 shows the evaluation results of the resin molding.
  • the resin molded body of Example 25 had good flame retardancy (JIS) and heat resistance.
  • mixture (a-4) 0.2 part of SFS and 5 parts of deionized water were mixed to obtain a mixture (a-4). 5.
  • mixture (a-5) 57.0 parts of MMA, 3.0 parts of BA, 0.1 part of DBP and 0.2 part of n-OM were mixed to obtain a mixture (a-5). 6).
  • Production of multi-structure acrylic copolymer particles (Rubber A) To a reaction vessel equipped with a reflux condenser, add 300 parts of ion-exchanged water, 0.09 part of sodium carbonate and 0.9 part of boric acid.
  • CR-570 as a phosphorus-based flame retardant (C)
  • t-hexylperoxypivalate as a polymerization initiator
  • X3 a polymerizable composition
  • a resin gasket was installed at the peripheral edge between two SUS plates arranged opposite to each other so that the gap between the two SUS plates was 4.1 mm, thereby producing a mold.
  • the polymerizable composition (X3) was prepared and allowed to stand for 168 hours, the polymerizable composition (X3) was poured into the mold and completely sealed with a resin gasket. The temperature was raised to 0 ° C.
  • Example 27 A resin molded body was obtained in the same manner as in Example 26 except that the addition amount of the impact resistance improver (D) was changed as shown in Table 8. Table 9 shows the evaluation results of the resin molding.
  • the resin molded body of Example 27 had good flame retardancy (JIS), weather resistance, and Charpy impact strength.
  • mixture (b-4) 0.2 part of SFS and 5 parts of deionized water were mixed to obtain a mixture (b-4). 5.
  • mixture (b-5) MMA 57.0 parts, MA 3.0 parts, DBP 0.1 part, and n-OM 0.2 part were mixed to obtain a mixture (b-5). 6).
  • Production of multi-structure acrylic copolymer particles (rubber B) After adding 300 parts of ion-exchanged water, 0.09 part of sodium carbonate and 0.9 part of boric acid to a reaction vessel equipped with a reflux condenser, the temperature was raised to 80 ° C.
  • Example 29 A resin molded body was obtained in the same manner as in Example 26 except that 7.5 parts of a commercially available acrylic block copolymer (trade name: Clarity, manufactured by Kuraray Co., Ltd.) was added as the impact resistance improver (D). . Table 9 shows the evaluation results of the resin molding.
  • the resin molded body of Example 29 had good flame retardancy (JIS), weather resistance, and Charpy impact strength.
  • Example 30 (1) Production of cured film (F) Curable composition comprising 40% by mass of polyacrylate 1 as polyfunctional monomer (F1) and 60% by mass of diacrylate 1 as polyfunctional monomer (F2) The product (f) was mixed with 1.5 parts by mass of BEE as a photopolymerization initiator as 100 parts by mass of the curable composition (f) (hereinafter, the curability after adding the photopolymerization initiator). The composition is also referred to as “curable composition (f)”). Next, the curable composition (f) is applied onto a mirror-like SUS304 plate, covered with a PET film having a thickness of 12 ⁇ m, and rubbed with a rubber roll having a JIS hardness of 40 ° on the PET film.
  • a layer made of the curable composition (f) was formed.
  • the SUS304 plate on which the layer of the curable composition (f) was formed was placed at a speed of 2 m / min at a position 20 cm below the fluorescent ultraviolet lamp (manufactured by Toshiba Corporation, trade name: FL40BL, output 40 W).
  • the curable composition (f) was irradiated with light from a fluorescent ultraviolet lamp through the PET film while passing through the film, and after curing, the PET film was peeled off.
  • the SUS304 plate on which the layer of the curable composition (f) after the curing treatment is formed is passed through a position 20 cm below the high-pressure mercury lamp (output 30 W / cm 2 ) at a speed of 3 m / min.
  • the curable composition (f) was irradiated with ultraviolet light from a high-pressure mercury lamp, and further cured to form a cured film (F) having a thickness of 20 ⁇ m on the SUS304 plate. The same operation was repeated to obtain two SUS304 plates on which a cured film (F) was formed.
  • CR-570 as a phosphorus-based flame retardant (C)
  • t-hexylperoxypivalate as a polymerization initiator
  • the polymerizable composition (X3) was poured into the mold and completely sealed with a resin gasket.
  • the polymerizable composition (X3) was polymerized by heating at 82 ° C. for 30 minutes and then at 130 ° C. for 30 minutes, and then cooled to room temperature.
  • the SUS plate was removed to obtain a plate-shaped resin laminate having a thickness of 3 mm.
  • the cut surface of the test piece was polished with a milling machine.
  • Table 11 shows the evaluation results of the resin laminate.
  • the obtained resin laminate had flame retardancy as evaluated by flame retardancy (JIS), had a heat resistance of 95 ° C., a weather resistance ( ⁇ YI) of 3, and a pencil hardness of 4H.
  • Example 31 A resin laminate was obtained in the same manner as in Example 30, except that the addition amount of the phosphorus-based flame retardant (C) was changed as described in Table 10. Table 11 shows the evaluation results of the obtained resin laminate.
  • the obtained resin laminate has good flame retardancy in evaluation of flame retardancy (JIS, UL94), heat resistance of 82 ° C., weather resistance ( ⁇ YI) of 3, and pencil hardness of 4H. there were.
  • Examples 32 and 33 A resin laminate was obtained in the same manner as in Example 30 except that the composition of the curable composition (f) of the cured film (F) and the addition amount of the phosphorus-based flame retardant (C) were as shown in Table 10.
  • Table 11 shows the evaluation results of the obtained resin laminate.
  • the resin laminate obtained in Example 32 has flame retardancy in evaluation of flame retardancy (JIS), heat resistance of 95 ° C., weather resistance ( ⁇ YI) of 3, and pencil hardness of 8H. there were.
  • the resin laminate obtained in Example 33 has good flame retardancy in evaluation of flame retardancy (JIS, UL94), heat resistance of 82 ° C., weather resistance ( ⁇ YI) of 3, and pencil The hardness was as good as 8H.
  • a (meth) acrylic resin composition having good heat resistance and further high flame retardancy
  • a resin molded body comprising the (meth) acrylic resin composition. It can.
  • Such a resin molded body can be suitably used for applications requiring high flame retardancy such as signboards.

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WO2023118486A1 (en) 2021-12-23 2023-06-29 Arkema France (meth)acrylic composition, composite material obtained from such a composition, method for producing said composition and uses thereof

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