WO2013161267A1 - Composition de résine méthacrylique - Google Patents

Composition de résine méthacrylique Download PDF

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Publication number
WO2013161267A1
WO2013161267A1 PCT/JP2013/002715 JP2013002715W WO2013161267A1 WO 2013161267 A1 WO2013161267 A1 WO 2013161267A1 JP 2013002715 W JP2013002715 W JP 2013002715W WO 2013161267 A1 WO2013161267 A1 WO 2013161267A1
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WO
WIPO (PCT)
Prior art keywords
methacrylic resin
methacrylate
mass
resin composition
methyl methacrylate
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PCT/JP2013/002715
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English (en)
Japanese (ja)
Inventor
啓之 小西
敦 松村
宙 小澤
卓郎 新村
日出美 栗田
英孝 田村
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株式会社クラレ
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Priority to JP2014512351A priority Critical patent/JP6046707B2/ja
Publication of WO2013161267A1 publication Critical patent/WO2013161267A1/fr

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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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate

Definitions

  • the present invention relates to a methacrylic resin composition. More specifically, the present invention is a thin-walled and large-area molded product with little coloring, high transparency, low haze, high impact strength, low saturated water absorption, small dimensional change, and good appearance.
  • the present invention relates to a methacrylic resin composition that can be obtained with high production efficiency.
  • Methacrylic resin is excellent in transparency, light resistance and surface hardness.
  • various optical members such as a light guide plate and a lens can be obtained.
  • a demand for a light-weight and wide-area liquid crystal display device is high, and correspondingly, an optical member is also required to be thin and wide. Furthermore, high accuracy is required for optical characteristics such as refractive index and retardation as the image quality of display devices increases. Thin-walled and large-area molded products are prone to greatly affect optical characteristics due to dimensional changes due to moisture absorption and heat. Therefore, a methacrylic resin composition that is a raw material for optical members is strongly required to have high transparency, low moisture absorption, high heat resistance, small dimensional change, high impact strength, high moldability, and the like.
  • Patent Document 1 discloses that a methacrylic acid ester or an acrylate ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in an ester portion, Acrylic acid ester or aromatic vinyl compound having 50 to 80 parts by weight of methyl acid, 5 to 40 parts by weight of N-substituted maleimide, 0 to 30 parts by weight of benzyl methacrylate, and a hydrocarbon group having 1 to 5 carbon atoms in the ester moiety
  • the absolute value of orientation birefringence of the obtained resin is less than 1 ⁇ 10 ⁇ 6 , the melt flow rate is 15 g / 10 min or more, and the bending fracture strength is 50 MPa.
  • Patent Document 2 discloses that polymerization is carried out using a methacrylate ester or acrylate ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester portion and methyl methacrylate as essential monomer components.
  • An optical element having a glass transition temperature of 120 ° C. or more obtained by washing the obtained resin in the presence of an organic solvent containing a fatty acid amide or a fatty acid ester having an endothermic peak temperature of 70 ° C. or more in a differential scanning calorimeter Resins for use are disclosed.
  • the (meth) acrylic resin disclosed in Patent Document 1 tends to be easily colored.
  • the composition described in the Example of patent document 2 was very brittle, and it was difficult to obtain a molded product with a thin wall and a large area. Therefore, the object of the present invention is to provide a molded product having a thin wall and a large area with little coloring, high transparency, low haze, high impact strength, low saturated water absorption, small dimensional change, and good appearance.
  • the object is to provide a methacrylic resin composition that can be obtained with high production efficiency.
  • [1] 30 to 87 mass% of structural units derived from methyl methacrylate, 10 to 50 mass% of structural units derived from cycloalkyl methacrylate, and 3 to 3 structural units derived from alkyl methacrylate other than methyl methacrylate Containing 99% by mass or more of methacrylic resin containing 20% by mass, A methacrylic resin composition having a melt flow rate of 5 g / 10 min or more under conditions of 230 ° C. and a load of 3.8 kg.
  • the methacrylic resin composition according to [1] or [2], wherein the alkyl methacrylate other than methyl methacrylate is a compound represented by the formula (1).
  • R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms
  • R 3 represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • [5] A monomer mixture composed of 30 to 87% by weight of methyl methacrylate, 10 to 50% by weight of cycloalkyl ester of methacrylic acid, and 3 to 20% by weight of alkyl ester of methacrylic acid other than methyl methacrylate,
  • a molded article comprising the methacrylic resin composition according to any one of [1] to [4].
  • [7] The molded article according to [6], wherein the ratio of the resin flow length to the thickness is 380 or more.
  • the methacrylic resin composition of the present invention contains a methacrylic resin.
  • the methacrylic resin used in the present invention contains 30 to 87% by mass, preferably 50 to 80% by mass, of structural units derived from methyl methacrylate among all monomer units.
  • the methacrylic resin used in the present invention contains 10 to 50% by mass, preferably 10 to 30% by mass, of structural units derived from methacrylic acid cycloalkyl ester, among all monomer units.
  • the number of carbon atoms in the cycloalkyl group in the methacrylic acid cycloalkyl ester is preferably 5 or more, and more preferably 5 to 12.
  • cycloalkyl methacrylate examples include cyclopentyl methacrylate, methyl cyclopentyl methacrylate, ethyl cyclopentyl methacrylate, cyclohexyl methacrylate, methyl cyclohexyl methacrylate, ethyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, cyclodecyl methacrylate, norbornyl methacrylate, Methyl norbornyl methacrylate, ethyl norbornyl methacrylate, isobornyl methacrylate, bornyl methacrylate, menthyl methacrylate, fentil methacrylate, adamantyl methacrylate, methyl adamantyl methacrylate, ethyl adamantyl methacrylate, dimethyl adamantyl methacrylate, methacrylic acid Dicycl
  • cyclopentyl methacrylate in terms of low hygroscopicity, cyclopentyl methacrylate, cyclohexyl methacrylate, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, norbornyl methacrylate, methyl norbornyl methacrylate, isobornyl methacrylate, bornyl methacrylate, methacrylic acid
  • Menthyl, fentyl methacrylate, adamantyl methacrylate, dimethyladamantyl methacrylate, dicyclopentanyl methacrylate and methyl dicyclopentanyl methacrylate are preferred, and dicyclopentanyl methacrylate is particularly preferred.
  • the methacrylic resin used in the present invention contains 3 to 20% by mass, preferably 5 to 15% by mass, of structural units derived from methacrylic acid alkyl esters other than methyl methacrylate among all monomer units.
  • the number of carbon atoms of the alkyl group in the methacrylic acid alkyl ester is 2 or more, preferably 2 to 12.
  • Examples of the alkyl methacrylate include ethyl methacrylate, propyl methacrylate, butyl methacrylate, t-butyl methacrylate, 2-methylbutyl methacrylate, 2-methylpentyl methacrylate, 2-ethylbutyl methacrylate, 3-methyl methacrylate. Examples include pentyl, 2-methylhexyl methacrylate, 3-methylhexyl methacrylate, 2-ethylhexyl methacrylate, and the like. Among these, the compound represented by Formula (1) is preferable.
  • R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms
  • R 3 represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • the methacrylic resin used in the present invention contains structural units derived from monomers other than these in addition to structural units derived from methyl methacrylate, methacrylic acid cycloalkyl ester and alkyl methacrylate other than methyl methacrylate. You may go out. Examples of such monomers include non-crosslinkable vinyl-based monomers having only one polymerizable alkenyl group in one molecule such as acrylate esters such as methyl acrylate, ethyl acrylate, norbornyl acrylate, and dicyclopentanyl acrylate. Monomer.
  • the amount of the structural unit derived from the monomer is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total monomer units.
  • the methacrylic resin has a weight average molecular weight (hereinafter sometimes abbreviated as Mw), preferably 50,000 to 200,000, more preferably 80,000 to 150,000, and particularly preferably 90,000 to 120,000.
  • Mw weight average molecular weight
  • Mw weight average molecular weight
  • the methacrylic resin has a weight average molecular weight / number average molecular weight ratio (hereinafter this ratio may be referred to as molecular weight distribution), preferably 1.7 to 3.0, more preferably 1.8 to 2. 8, particularly preferably 1.9 to 2.7. If the molecular weight distribution is small, the molding processability of the methacrylic resin composition tends to decrease. When the molecular weight distribution is large, the impact resistance of the molded product obtained from the methacrylic resin composition tends to be lowered, and it tends to be brittle.
  • a weight average molecular weight and a number average molecular weight are molecular weights of standard polystyrene conversion measured by GPC (gel permeation chromatography). The molecular weight and molecular weight distribution of the methacrylic resin can be controlled by adjusting the types and amounts of the polymerization initiator and the chain transfer agent.
  • the methacrylic resin is obtained by polymerizing a monomer mixture containing at least the above-mentioned mass ratio of methyl methacrylate, cycloalkyl methacrylate, and alkyl methacrylate other than methyl methacrylate.
  • the methacrylic acid raw material methyl methacrylate, methacrylic acid cycloalkyl ester, methacrylic acid alkyl ester other than methyl methacrylate, and other monomers as optional components preferably have a yellow index of 2 or less, preferably 1 or less. It is more preferable that When the monomer yellow index is small, when the resulting (meth) acrylic resin composition is molded, a thin and wide-area molded product with little residual distortion and little coloration can be obtained with high production efficiency. Cheap. As will be described later, in the bulk polymerization or solution polymerization reaction for producing a methacrylic resin, the polymerization conversion rate is not so high, so that unreacted monomers remain in the polymerization reaction solution.
  • Unreacted monomer is recovered from the polymerization reaction solution and used again for the polymerization reaction.
  • the yellow index of the recovered monomer may increase due to heat applied during recovery.
  • the recovered monomer is preferably purified by an appropriate method to reduce the yellow index.
  • the yellow index is a value measured according to JIS Z-8722 using a colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • the polymerization reaction of the monomer mixture is carried out by suspension polymerization, bulk polymerization or solution polymerization, preferably suspension polymerization or bulk polymerization.
  • the polymerization reaction is initiated by adding a polymerization initiator to the monomer mixture.
  • the molecular weight etc. of the polymer obtained can be adjusted by adding a chain transfer agent to a monomer mixture as needed.
  • the monomer mixture has a dissolved oxygen content of preferably 10 ppm or less, more preferably 5 ppm or less, further preferably 4 ppm or less, and most preferably 3 ppm or less. When the amount of dissolved oxygen is in such a range, the polymerization reaction proceeds smoothly, and it becomes easy to obtain a molded product without silver or coloring.
  • the polymerization initiator used in the present invention is not particularly limited as long as it generates a reactive radical.
  • t-hexyl peroxyisopropyl monocarbonate t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate soot
  • t-butyl peroxypivalate T-hexylperoxypivalate
  • t-butylperoxyneodecanoate t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate
  • 1 1-bis (t-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2′-azobis (2-methylpropionitrile), 2, 2′-azobis (2-methylbutyronit
  • t-hexylperoxy 2-ethylhexanoate 1,1-bis (t-hexylperoxy) cyclohexane, and dimethyl 2,2'-azobis (2-methylpropionate) are preferred.
  • the polymerization initiator preferably has a one-hour half-life temperature of 60 to 140 ° C, more preferably 80 to 120 ° C.
  • the polymerization initiator used for bulk polymerization preferably has a hydrogen abstraction ability of 30% or less, more preferably 20% or less, and even more preferably 10% or less.
  • These polymerization initiators can be used alone or in combination of two or more.
  • the addition amount and addition method of the polymerization initiator are not particularly limited as long as they are appropriately set according to the purpose.
  • the amount of the polymerization initiator used for bulk polymerization is preferably 0.0001 to 0.02 parts by mass, more preferably 0.001 to 0.01 parts by mass with respect to 100 parts by mass of the monomer mixture. is there.
  • the hydrogen abstraction ability can be known from technical data (for example, Non-Patent Document 1) of the polymerization initiator manufacturer. Further, it can be measured by a radical trapping method using ⁇ -methylstyrene dimer, that is, ⁇ -methylstyrene dimer trapping method. The measurement is generally performed as follows. First, the polymerization initiator is cleaved in the presence of ⁇ -methylstyrene dimer as a radical trapping agent to generate radical fragments. Among the generated radical fragments, radical fragments having a low hydrogen abstraction ability are added to and trapped by the double bond of ⁇ -methylstyrene dimer.
  • a radical fragment having a high hydrogen abstraction capacity abstracts hydrogen from cyclohexane to generate a cyclohexyl radical, and the cyclohexyl radical is added to and trapped by the double bond of ⁇ -methylstyrene dimer to generate a cyclohexane trapping product. Therefore, the ratio (mole fraction) of radical fragments having a high hydrogen abstraction capacity with respect to the theoretical radical fragment generation amount, which is obtained by quantifying cyclohexane or cyclohexane-trapped product, is defined as the hydrogen abstraction capacity.
  • chain transfer agents can be used alone or in combination of two or more.
  • monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan and polyfunctional mercaptans such as pentaerythritol tetrakisthiopropionate are preferable, and polyfunctional mercaptans (multivalent thiols) are more preferable.
  • the amount of chain transfer agent used is preferably 0.1 to 1 part by weight, more preferably 0.2 to 0.8 part by weight, and still more preferably 0.3 to 0 part per 100 parts by weight of the monomer mixture. .6 parts by mass.
  • the solvent used in the solution polymerization is not particularly limited as long as it has a solubility in the monomer mixture as a raw material and the product methacrylic resin, but aromatic hydrocarbons such as benzene, toluene, and ethylbenzene are not limited. preferable. These solvents can be used alone or in combination of two or more.
  • the amount of the solvent to be used is preferably 0 to 100 parts by mass, more preferably 0 to 90 parts by mass with respect to 100 parts by mass of the monomer mixture. The greater the amount of solvent used, the lower the viscosity of the reaction solution and the better the handleability but the lower the productivity.
  • the polymerization conversion rate of the monomer mixture in the bulk polymerization method or the solution polymerization method is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 35 to 65% by mass.
  • the polymerization conversion rate is in such a range, it is easy to adjust characteristics such as the melt flow rate to a range described later. If the polymerization conversion rate is too high, a large stirring power tends to be required for increasing the viscosity. If the polymerization conversion rate is too low, devolatilization tends to be insufficient, and a molded product made of methacrylic resin tends to cause poor appearance such as silver.
  • Examples of the apparatus for performing the bulk polymerization method or the solution polymerization method include a tank reactor with a stirrer, a tube reactor with a stirrer, and a tube reactor having a static stirring ability. One or more of these apparatuses may be used, or two or more different reactors may be used in combination.
  • the apparatus may be either a batch type or a continuous flow type.
  • the stirrer to be used can be selected according to the type of the reactor. Examples of the stirrer include a dynamic stirrer and a static stirrer.
  • the most suitable apparatus for obtaining the methacrylic resin used in the present invention is one having at least one continuous flow tank reactor. A plurality of continuous flow tank reactors may be connected in series or in parallel.
  • a stirring means for stirring the liquid in the reaction tank
  • a supply unit for supplying a monomer mixture or a polymerization auxiliary material to the reaction tank
  • a reaction product is extracted from the reaction tank.
  • an extraction part In the continuous flow reaction, the amount supplied to the reaction vessel and the amount withdrawn from the reaction vessel are balanced so that the amount of liquid in the reaction vessel becomes substantially constant.
  • the amount of the liquid in the reaction tank is preferably 1/4 to 3/4, more preferably 1/3 to 2/3, with respect to the volume of the reaction tank.
  • the agitation means include a Max blend type agitation device, an agitation device having a grid-like blade rotating around a vertical rotation shaft disposed in the center, a propeller type agitation device, and a screw type agitation device.
  • a Max blend type stirring apparatus is preferably used from the point of uniform mixing property.
  • Methyl methacrylate, methacrylic acid cycloalkyl ester, alkyl methacrylate other than methyl methacrylate and other optional monomers as well as polymerization initiator and chain transfer agent are mixed together before supplying them to the reactor. May be supplied to the reaction vessel, or may be supplied separately to the reaction vessel. In the present invention, a method of mixing all the components before supplying them to the reaction vessel and supplying them to the reaction vessel is preferable.
  • methyl methacrylate, cycloalkyl methacrylate, alkyl methacrylate other than methyl methacrylate, polymerization initiator and chain transfer agent is preferably performed in an inert atmosphere such as nitrogen gas.
  • pipes are respectively connected from tanks storing methyl methacrylate, methacrylic acid cycloalkyl ester, alkyl methacrylate other than methyl methacrylate, polymerization initiator and chain transfer agent. It is preferable to supply to the mixer provided in the front
  • the mixer can be equipped with a dynamic stirrer or a static stirrer.
  • the temperature during the polymerization reaction is preferably 90 to 135 ° C, more preferably 95 to 130 ° C.
  • the polymerization reaction time is preferably 0.5 to 4 hours, and more preferably 1 to 3 hours.
  • the polymerization reaction time is an average residence time in the reactor. If the polymerization reaction time is too short, the required amount of polymerization initiator increases. Further, increasing the amount of the polymerization initiator makes it difficult to control the polymerization reaction, and tends to make it difficult to control the molecular weight. On the other hand, if the polymerization reaction time is too long, it takes time for the reaction to reach a steady state, and the productivity tends to decrease.
  • the polymerization is preferably performed in an inert gas atmosphere such as nitrogen gas.
  • the removal method is not particularly limited, but heating devolatilization is preferable.
  • the devolatilization method include an equilibrium flash method and an adiabatic flash method. Particularly in the adiabatic flash method, devolatilization is preferably performed at a temperature of 200 to 300 ° C., more preferably 220 to 270 ° C. Below 200 ° C., it takes time for devolatilization, and devolatilization tends to be insufficient. When devolatilization is insufficient, appearance defects such as silver may occur in the molded product. On the other hand, if the temperature exceeds 300 ° C., the methacrylic resin composition tends to be colored due to oxidation, burning, or the like.
  • the amount of the methacrylic resin contained in the methacrylic resin composition of the present invention is 99% by mass or more, preferably 99.5% by mass or more, more preferably 99.8% by mass or more based on the whole methacrylic resin composition. .
  • the methacrylic resin composition of the present invention may contain various additives as necessary in an amount of 0.5% by mass or less, preferably 0.2% by mass or less. When there is too much content of an additive, external appearance defects, such as silver, may be produced in a molded article.
  • Additives include antioxidants, thermal degradation inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes and pigments, light diffusing agents, organic dyes , Matting agents, impact resistance modifiers, phosphors and the like.
  • the antioxidant alone has an effect of preventing oxidative deterioration of the resin in the presence of oxygen.
  • examples thereof include phosphorus antioxidants, hindered phenol antioxidants, and thioether antioxidants. These antioxidants can be used alone or in combination of two or more. Among these, from the viewpoint of preventing the deterioration of optical properties due to coloring, phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable, and the combined use of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable. preferable.
  • the ratio is not particularly limited, but is preferably a mass ratio of phosphorus antioxidant / hindered phenol antioxidant, preferably 1/5. ⁇ 2 / 1, more preferably 1 ⁇ 2 to 1/1.
  • phosphorus antioxidants examples include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (Asahi Denka Co., Ltd .; trade name: ADK STAB HP-10), Tris (2,4-dit -Butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals; trade name: IRUGAFOS168) is preferred.
  • pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals; trade name IRGANOX 1010)
  • Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Ciba Specialty Chemicals; trade name IRGANOX 1076) is preferred.
  • the thermal degradation inhibitor can prevent thermal degradation of the resin by scavenging polymer radicals generated when exposed to high heat in a substantially oxygen-free state.
  • the thermal degradation inhibitor include 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilizer GM), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumitizer GS) preferable.
  • the ultraviolet absorber is a compound having an ability to absorb ultraviolet rays.
  • the ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy.
  • Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, and the like. These can be used alone or in combination of two or more.
  • benzotriazoles or ultraviolet absorbers having a maximum molar extinction coefficient ⁇ max at a wavelength of 380 to 450 nm of 1200 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less are preferable.
  • Benzotriazoles have a high effect of suppressing deterioration of optical characteristics such as coloring due to ultraviolet irradiation, and therefore, the ultraviolet absorber used when the methacrylic resin composition of the present invention is applied to applications requiring the above characteristics. As preferred.
  • benzotriazoles examples include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN329), 2 -(2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN234) is preferred.
  • the ultraviolet absorber having the maximum molar extinction coefficient ⁇ max at wavelengths of 380 to 450 nm of 1200 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less can suppress the yellowness of the obtained molded product.
  • the ultraviolet absorber is preferable as an ultraviolet absorber used when the methacrylic resin composition of the present invention is applied to applications requiring such characteristics.
  • the maximum value ⁇ max of the molar extinction coefficient of the ultraviolet absorber is measured as follows. Add 10.00 mg of UV absorber to 1 L of cyclohexane and dissolve it so that there is no undissolved material by visual observation. This solution is poured into a 1 cm ⁇ 1 cm ⁇ 3 cm quartz glass cell, and the absorbance at a wavelength of 380 to 450 nm is measured using a U-3410 type spectrophotometer manufactured by Hitachi, Ltd. The maximum value ⁇ max of the molar extinction coefficient is calculated from the molecular weight (Mw) of the ultraviolet absorber and the maximum value (A max ) of the measured absorbance by the following formula.
  • ⁇ max [A max / (10 ⁇ 10 ⁇ 3 )] ⁇ Mw
  • an ultraviolet absorber having a maximum molar extinction coefficient ⁇ max at a wavelength of 380 to 450 nm of 1200 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less, 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan, Inc .; Trade name Sundeyuboa VSU).
  • benzotriazoles are preferably used from the viewpoint of suppressing resin degradation due to ultraviolet irradiation.
  • the light stabilizer is a compound that is said to have a function of capturing radicals generated mainly by oxidation by light.
  • Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.
  • the mold release agent is a compound having a function of facilitating release of the molded product from the mold.
  • the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.
  • the ratio is not particularly limited, but the mass ratio of higher alcohols / glycerin fatty acid monoester is preferably 2.5 / 1 to 3.5 / 1. The preferred range is 2.8 / 1 to 3.2 / 1.
  • the polymer processing aid is a compound that exhibits an effect on thickness accuracy and thinning when a methacrylic resin composition is molded.
  • the polymer processing aid is polymer particles having a particle diameter of 0.05 to 0.5 ⁇ m, which can be usually produced by an emulsion polymerization method.
  • the polymer particles may be single layer particles composed of polymers having a single composition ratio and single intrinsic viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. May be.
  • particles having a two-layer structure having a polymer layer having a low intrinsic viscosity in the inner layer and a polymer layer having a high intrinsic viscosity of 5 dl / g or more in the outer layer are preferable.
  • the polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g as a whole. If the intrinsic viscosity is too small, the effect of improving moldability is low. When the intrinsic viscosity is too large, the melt fluidity of the methacrylic resin composition is likely to be lowered.
  • An impact modifier may be added to the methacrylic resin composition of the present invention.
  • the impact modifier include a core-shell type modifier containing acrylic rubber or diene rubber as a core layer component; a modifier containing a plurality of rubber particles, and the like.
  • the organic dye a compound having a function of converting ultraviolet rays that are harmful to the resin into visible light is preferably used.
  • the light diffusing agent and matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, and barium sulfate.
  • the phosphor include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent brightener, and a fluorescent bleach.
  • additives may be added to a polymerization reaction solution when producing a methacrylic resin, or may be added to a methacrylic resin produced by a polymerization reaction.
  • the methacrylic resin composition of the present invention has a melt flow rate of 5 g / 10 min or more, preferably 8 to 35 g / 10 min, more preferably 10 to 32 g / 10 min under the conditions of 230 ° C. and 3.8 kg load.
  • the melt flow rate is a value measured under conditions of 230 ° C., 3.8 kg load, and 10 minutes in accordance with JIS K7210.
  • the preferred methacrylic resin composition of the present invention has a saturated water absorption rate of preferably 1.6% by mass or less, more preferably 1.5% by mass or less. Further, in the preferred methacrylic resin composition of the present invention, the yellow index (YI) of the sheet thickness of 3 mm of the injection molded product obtained at a cylinder temperature of 260 ° C. and a molding cycle of 1 minute is preferably 2 or less, more preferably 1. 5 or less, more preferably 1 or less.
  • Various molded products can be obtained by subjecting the methacrylic resin composition of the present invention to melt heating molding by a method such as injection molding, compression molding, extrusion molding, or vacuum molding.
  • the methacrylic resin composition of the present invention has a high production efficiency for a molded product having a high transparency, a low haze, a high impact strength, a low saturated water absorption, a small dimensional change, and a good appearance with a thin wall and a large area. Can be offered at.
  • Examples of molded articles made of the methacrylic resin composition of the present invention include billboard parts such as advertising towers, stand signs, sleeve signs, column signs, and rooftop signs; display parts such as showcases, partition plates, and store displays; fluorescent lamps Lighting parts such as covers, mood lighting covers, lamp shades, light ceilings, light walls, chandeliers; interior parts such as pendants and mirrors; doors, domes, safety window glass, partitions, staircases, balconies, balconies, and leisure buildings Construction parts such as roofs; aircraft windshields, pilot visors, motorcycles, motor boat windshields, bus shading plates, automotive side visors, rear visors, head wings, headlight covers, and other transportation equipment related parts; Electronic such as covers, TV protective masks, vending machines Instrument parts; Medical equipment parts such as incubators and X-ray parts; Machine-related parts such as machine covers, instrument covers, experimental devices, rulers, dials, observation windows; LCD protective plates, light guide plates, light guide films, Fresnel lenses, Optical components such as lenticular
  • Film members Household appliances such as washing machine canopies and control panels, rice cooker top panels; other greenhouses, large aquariums, box aquariums, clock panels, bathtubs, sanitary, desk mats, game parts, toys, For example, a mask for protecting the face during welding.
  • a thin injection molded product having a thickness of 1 mm or less is preferable, and is particularly suitable for a thin injection molding product having a resin flow length to thickness ratio of 380 or more.
  • a light guide plate is a good example of a thin-walled and large-area injection-molded product.
  • the resin flow length is the distance between the gate of the injection mold and the inner wall of the mold farthest from the gate.
  • the resin flow length in the film gate is the distance between the runner and sprue attachment part of the injection mold and the inner wall of the mold farthest from the attachment part.
  • the gate of the mold for obtaining a molded product having a thin wall and a large area according to the present invention is preferably a film gate.
  • the film gate is cut with a cutting machine and finished with a router or the like.
  • a pinpoint gate (also called a center gate or a pin gate) can be used as a gate of a mold for obtaining a molded product according to the present invention.
  • the pinpoint gate is automatically cut off from the runner, and there is little work such as finishing.
  • Monomers, inorganic salts and suspension dispersants in Examples and Comparative Examples are MMA for methyl methacrylate, TCDMA for dicyclopentanyl methacrylate, MA for methyl acrylate, EMA for ethyl methacrylate, 2-methacrylic acid 2- Ethylhexyl 2-EHMA, N-cyclohexylmaleimide CHMI, 2,2′-azobis (2-methylpropionitrile AIBN, n-octyl mercaptan OM, pentaerythritol tetrakisthiopropionate PETP, diphosphate Sodium hydrogen is described as (A-1), sodium (2) hydrogen phosphate as (A-2), and sodium sulfate as (A-3).
  • the suspension dispersant (B) used in the examples and comparative examples was prepared by charging 100 g of sodium styrene p-sulfonate, 20 g of sodium methacrylate, 30 g of methyl methacrylate, and 600 g of ion-exchanged water into a 2 L separable flask. Under stirring, the temperature was raised to 60 ° C., 0.2 g of ammonium persulfate was added and held for 3 hours, then held at 70 ° C. for 3 hours and then cooled to obtain a colorless and transparent solution of 37 Pa ⁇ s (25 ° C.). Obtained.
  • the suspension dispersant (C) used in Examples and Comparative Examples was prepared by charging 112 g of potassium hydroxide and 300 g of ion-exchanged water into a 2 L separable flask and raising the temperature to 50 ° C. with stirring in a nitrogen atmosphere. Add 200 g of methyl methacrylate. The internal temperature rose due to saponification heat generation, held at 70 ° C. for 1.5 hours, then cooled to 60 ° C., 0.2 g of ammonium persulfate was added, 5 hours later, 500 g of ion-exchanged water was added and diluted, and 2.0 Pa Obtained as a cloudy solution of s (25 ° C.).
  • the monomer mixture was placed in a quartz cell having a length of 10 mm, a width of 10 mm, and a length of 45 mm, and the transmittance in the 10 mm width direction was measured using a colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. From the measured values obtained, XYZ values were determined according to the method described in JIS Z-8722, and yellowness (YI) was calculated according to the method described in JIS K-7105.
  • Melt flow rate According to JIS K7210, it measured on 230 degreeC, the 3.8kg load, and the conditions for 10 minutes.
  • the flat plate T was placed in a thermostat having a temperature of 60 ° C. and a relative humidity of 90% and left in the atmosphere for 500 hours. The flat plate was taken out from the thermostat and the length dimension was measured. The dimensional change rate from the dimension in the length direction before putting in the thermostat was calculated.
  • Example 1 A monomer mixture was prepared by adding 67 parts by mass of MMA, 20 parts by mass of TCDMA, 10 parts by mass of EMA, and 3 parts by mass of MA. The yellow index of the monomer mixture was 0.7. To 100 parts by mass of the monomer mixture, 0.06 parts by mass of AIBN and 0.3 parts by mass of OM were added and dissolved to obtain a raw material solution.
  • the polymerization system did not foam, and almost no polymer adhered to the wall of the polymerization tank or the stirring blade was observed.
  • the obtained polymer dispersion was washed with an appropriate amount of ion-exchanged water and dehydrated to obtain a uniform bead-like methacrylic resin composition having an average particle size of 0.26 mm.
  • the bead-like methacrylic resin was subjected to evaluation after being dried at 80 ° C. for 4 hours or more with a hot air dryer.
  • the bead-like methacrylic resin was supplied to a twin screw extruder controlled at 260 ° C., and volatile components mainly composed of unreacted monomers were separated and removed, and the resin component was extruded into a strand shape.
  • the strand was cut with a pelletizer to obtain a pellet-shaped methacrylic resin composition.
  • the evaluation results of the obtained methacrylic resin composition are shown in Table 1.
  • Examples 2 to 3 and Comparative Examples 1 to 7 A pellet-shaped methacrylic resin composition was obtained in the same manner as in Example 1 except that the formulation shown in Table 1 was changed. The evaluation results of these methacrylic resin compositions are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne une composition de résine méthacrylique qui contient 99 % en masse ou plus d'une résine méthacrylique et présente un indice de fluage à 230 °C/3,8 kg de charge de 5 g/10 min ou plus, ladite résine méthacrylique comprenant : de 30 à 87 % en masse d'un motif structural dérivé de méthacrylate de méthyle ; de 10 à 50 % en masse d'un motif structural dérivé d'un méthacrylate de cycloalkyle ; et de 3 à 20 % en masse d'un motif structural dérivé d'un méthacrylate d'alkyle autre que le méthacrylate de méthyle.
PCT/JP2013/002715 2012-04-27 2013-04-22 Composition de résine méthacrylique WO2013161267A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2015064575A1 (fr) * 2013-10-28 2015-05-07 株式会社クラレ Corps moulé en forme de plaque
WO2015064576A1 (fr) * 2013-10-28 2015-05-07 株式会社クラレ Procédé de production d'une composition de résine méthacrylique

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JPH06279706A (ja) * 1993-03-29 1994-10-04 Mitsubishi Rayon Co Ltd 被覆材組成物
JP2004291561A (ja) * 2003-03-28 2004-10-21 Toyo Ink Mfg Co Ltd インクジェット受容シート
JP2004345262A (ja) * 2003-05-23 2004-12-09 Toyo Ink Mfg Co Ltd 溶剤系インク用インクジェット受容シート
JP2012031351A (ja) * 2010-08-03 2012-02-16 Mitsubishi Rayon Co Ltd アクリル樹脂板の製造方法、アクリル樹脂板、アクリル樹脂積層体及び表示装置

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US8163844B2 (en) * 2006-09-15 2012-04-24 Kuraray Co., Ltd. Methacrylic resin composition, resin modifier, and molded article

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH06279706A (ja) * 1993-03-29 1994-10-04 Mitsubishi Rayon Co Ltd 被覆材組成物
JP2004291561A (ja) * 2003-03-28 2004-10-21 Toyo Ink Mfg Co Ltd インクジェット受容シート
JP2004345262A (ja) * 2003-05-23 2004-12-09 Toyo Ink Mfg Co Ltd 溶剤系インク用インクジェット受容シート
JP2012031351A (ja) * 2010-08-03 2012-02-16 Mitsubishi Rayon Co Ltd アクリル樹脂板の製造方法、アクリル樹脂板、アクリル樹脂積層体及び表示装置

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015064575A1 (fr) * 2013-10-28 2015-05-07 株式会社クラレ Corps moulé en forme de plaque
WO2015064576A1 (fr) * 2013-10-28 2015-05-07 株式会社クラレ Procédé de production d'une composition de résine méthacrylique
JPWO2015064575A1 (ja) * 2013-10-28 2017-03-09 株式会社クラレ 板状成形体

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