WO2015041311A1 - Resin composition and molded article thereof - Google Patents
Resin composition and molded article thereof Download PDFInfo
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- WO2015041311A1 WO2015041311A1 PCT/JP2014/074791 JP2014074791W WO2015041311A1 WO 2015041311 A1 WO2015041311 A1 WO 2015041311A1 JP 2014074791 W JP2014074791 W JP 2014074791W WO 2015041311 A1 WO2015041311 A1 WO 2015041311A1
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- 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
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
Definitions
- the present invention relates to a resin composition and a molded product thereof. More specifically, the present invention relates to a resin composition that hardly forms a gel during melt molding and has excellent heat resistance, and a molded product thereof.
- Methacrylic resin is excellent in transparency, scratch resistance, weather resistance and the like.
- This methacrylic resin may contain a lubricant for the purpose of improving releasability (for example, Patent Document 1).
- Patent Document 1 On the other hand, in order to improve the heat resistance of a methacrylic resin, it has been proposed to contain a unit derived from a (meth) acrylic acid alicyclic hydrocarbon ester (for example, Patent Document 2).
- JP 2012-180454 A JP-A-61-176901
- An object of the present invention is to provide a resin composition that hardly forms a gel during melt molding and has excellent heat resistance, and a molded product thereof.
- Lubricant (x) consisting of at least one selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters having no two or more hydroxyl groups in one molecule
- x 0.001 parts by mass or more 2 parts by mass or less
- a resin composition comprising 0 to 0.1 parts by mass of a lubricant (y1) comprising a monoglyceride of a saturated fatty acid having 10 to 24 carbon atoms.
- Lubricant (x) consisting of at least one selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters having no two or more hydroxyl groups in one molecule
- x 0.001 parts by mass or more 2 parts by mass or less
- a resin composition comprising 0 to 0.1 parts by mass of a lubricant (y2) comprising a fatty acid ester having two or more hydroxyl groups in one molecule.
- the lubricant (x) comprises at least one selected from the group consisting of aliphatic monohydric alcohols having 12 to 18 carbon atoms and saturated fatty acids having 16 to 24 carbon atoms. 6].
- [9] The resin composition according to any one of [1] to [8], wherein a saturated water absorption in water at 23 ° C. is 0.3 to 1.8% by mass.
- thermoplastic resin composition having a glass transition temperature of 130 ° C. or higher and 160 ° C. or lower is a resin composition containing polycarbonate.
- the resin composition according to the present invention has excellent heat resistance, and no gel is formed during melt molding. Furthermore, the resin composition according to the present invention has good adhesion to a molding roll and releasability (a property that does not cause sticking or seizure on the surface of the mold). A molded product formed by melt-molding the resin composition according to the present invention can be suitably used for an optical member or the like because it has few foreign matter defects and a good appearance.
- the resin composition according to the present invention contains a copolymer (a) and a lubricant (x).
- the copolymer (a) is composed of a structural unit derived from a methacrylic acid alicyclic hydrocarbon ester and a structural unit derived from another monomer.
- the methacrylic acid alicyclic hydrocarbon ester constituting the copolymer (a) used in the present invention is a compound represented by the formula (I).
- methacrylic acid alicyclic hydrocarbon esters examples include methacrylic acid monocyclic aliphatics such as cyclohexyl methacrylate, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, cyclopentyl methacrylate, cycloheptyl methacrylate, menthyl methacrylate, and the like.
- the content of structural units derived from methacrylic acid alicyclic carbon hydrogen ester is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, and still more preferably. Is 30 to 40% by mass.
- the amount is less than the above range, the heat resistance of the resin composition may be inferior.
- the impact resistance of the resin composition may be inferior.
- the other monomer constituting the copolymer (a) used in the present invention is not particularly limited as long as it can be copolymerized with a methacrylic acid alicyclic hydrocarbon ester.
- Such other monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, acrylic Amyl acid, Isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, cyclohexyl acrylate, norbornenyl acrylate, isobornyl acrylate, benzyl acrylate, acrylic acid Acrylic esters such as phenoxyethyl, 2-hydroxyethyl acrylate, 2-e
- the content of structural units derived from methyl methacrylate is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and still more preferably 60 to 70% by mass. If the content of the structural unit derived from methyl methacrylate is less than the above range, the transparency, scratch resistance and weather resistance of the resin composition may be inferior. When the content rate of the structural unit derived from methyl methacrylate is more than the above range, the heat resistance of the resin composition may be inferior.
- the content of structural units derived from monomers other than methacrylic acid alicyclic hydrocarbon ester and methyl methacrylate is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass. It is as follows.
- the copolymer (a) used in the present invention has a glass transition temperature of preferably 115 ° C to 150 ° C, more preferably 130 ° C to 150 ° C, and further preferably 140 ° C to 150 ° C.
- the resin composition has a good balance of heat resistance and impact resistance.
- the resin composition and a sheet-like laminate of thermoplastic resins such as polycarbonate Warpage of the body (hereinafter sometimes referred to as a laminated sheet) under high temperature and high humidity is suppressed.
- the copolymer (a) used in the present invention has a weight average molecular weight of preferably 40,000 or more and 500,000 or less, more preferably 70,000 or more and 300,000 or less, and still more preferably 100,000 or more and 200,000. 000 or less.
- the weight average molecular weight of the copolymer (a) is within the above range, the resin composition is excellent in molding processability, and the obtained molded product is excellent in the balance of scratch resistance and heat resistance.
- the ratio of the weight average molecular weight to the number average molecular weight (sometimes referred to as Mw / Mn) is preferably 1.7 or more and 2.6 or less, more preferably It is 1.7 or more and 2.3 or less, More preferably, it is 1.7 or more and 2.0 or less.
- 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 weight average molecular weight, number average molecular weight, and Mw / Mn of the copolymer (a) can be controlled by adjusting the types and amounts of the polymerization initiator and chain transfer agent described later.
- the yellow index of the monomer mixture subjected to polymerization is preferably 2 or less, and more preferably 1 or less. If the yellow index of the monomer mixture is small, when the resulting resin composition is molded, a molded product with little coloration can be easily obtained with high production efficiency.
- the yellow index is a yellowness value calculated in accordance with JIS K 7373 based on a value measured in accordance with JIS 87 Z8722 using a colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. .
- the amount of dissolved oxygen in the monomer mixture is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 4 ppm or less, and particularly preferably 3 ppm or less.
- 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 production of the copolymer (a) used in the present invention is not particularly limited by the polymerization method.
- Examples include suspension polymerization, (continuous) bulk polymerization, solution polymerization, and emulsion polymerization.
- the polymerization method is preferably performed by radical polymerization. Of these polymerization methods, the suspension polymerization method or the (continuous) bulk polymerization method is preferable, and the suspension polymerization method is more preferable from the viewpoints of productivity and thermal decomposition resistance.
- the polymerization reaction is initiated by a polymerization initiator added with the monomer mixture.
- the weight average molecular weight of the copolymer (a) obtained, a number average molecular weight, and molecular weight distribution can be adjusted by adding a chain transfer agent to a monomer mixture as needed.
- the polymerization initiator used for the production of the copolymer (a) 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-tetramethylbutyl peroxy 2-ethylhexanoate, 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-
- t-hexylperoxy 2-ethylhexanoate 1,1-bis (t-hexylperoxy) cyclohexane, and dimethyl 2,2'-azobis (2-methylpropionate) are preferable.
- Such a polymerization initiator has a one-hour half-life temperature of preferably 60 to 140 ° C., more preferably 80 to 120 ° C.
- 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 in the suspension polymerization method is preferably 0.0001 to 0.1 parts by mass, more preferably 0.001 to 0.07 parts by mass with respect to 100 parts by mass of the monomer mixture. Part.
- the chain transfer agent used for the production of the copolymer (a) is not particularly limited.
- n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bisthiopropionate, butanediol bisthioglycolate, butanediol bisthiol Alkyl mercaptans such as propionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropane tris- ( ⁇ -thiopropionate), pentaerythritol tetrakisthiopropionate; ⁇ -methylstyrene Dimer; terpinolene and the like can be mentioned.
- alkyl mercaptans such as n-octyl mercaptan and pentaerythritol tetrakisthiopropionate are preferred.
- chain transfer agents can be used alone or in combination of two or more.
- 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.
- Each monomer, polymerization initiator, and chain transfer agent used in the production of the copolymer (a) may be mixed together and supplied to the reaction vessel, or they may be separately supplied to the reaction vessel. May be supplied. In the present invention, a method of mixing all and supplying the mixture to the reaction vessel is preferable.
- the lubricant is a known additive that is added to the resin in order to impart lubricity and releasability.
- Known lubricants include higher alcohol lubricants, hydrocarbon lubricants, fatty acid lubricants, fatty acid metal salt lubricants, aliphatic amide lubricants, ester lubricants, and the like.
- the lubricant (x) used in the present invention is selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters having no two or more hydroxyl groups in one molecule.
- higher alcohols examples include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and oleyl alcohol.
- the higher alcohol used in the present invention is preferably an aliphatic monohydric alcohol, more preferably an aliphatic monohydric alcohol having 12 to 18 carbon atoms, from the viewpoint of high anti-friction properties and less mold and roll stains. Further, a saturated aliphatic monohydric alcohol having 12 to 18 carbon atoms is more preferable, and a saturated aliphatic monohydric alcohol having 16 to 18 carbon atoms is still more preferable.
- the hydrocarbon is preferably an aliphatic hydrocarbon having 12 or more carbon atoms from the viewpoint of high antifriction and releasability.
- Commercially available products such as aliphatic hydrocarbons such as liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin and polyolefin wax; partial oxides of aliphatic hydrocarbons; halides of aliphatic hydrocarbons can be used. Even in the case of these commercially available mixtures, the aliphatic hydrocarbons contained preferably have an average number of carbon atoms of 12 or more.
- fatty acids examples include lauric acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, erucic acid, arachidonic acid, and 12-hydroxystearic acid.
- the fatty acid used in the present invention is preferably a fatty acid having 10 or more carbon atoms, more preferably a fatty acid having 16 to 24 carbon atoms, more preferably a carbon atom, from the viewpoint of high anti-friction properties and less mold and roll stains. Saturated fatty acids of several 16 to 24 are more preferred.
- fatty acid metal salts include cadmium stearate, cadmium laurate, cadmium ricinoleate, cadmium naphthenate, cadmium 2-ethylhexoate, barium stearate, barium laurate, barium ricinoleate, barium naphthenate, barium 2-ethylhexoate, Calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate, zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexoate, lead stearate, dibasic lead stearate, lead naphthenate, tin stearate , Aluminum stearate, magnesium stearate and the like.
- the fatty acid constituting the fatty acid metal salt is preferably a fatty acid having 10 or more carbon atoms, more preferably a fatty acid having 16 to 24 carbon atoms, from the viewpoint of high anti-friction properties and less mold dirt and roll dirt. More preferred are saturated fatty acids having 16 to 24 carbon atoms.
- the metal constituting the fatty acid metal salt calcium, magnesium, zinc, lead, tin, iron, cadmium, aluminum, barium, cobalt, nickel, manganese, strontium, titanium, vanadium, from the viewpoint of stability and antifriction And at least one metal selected from the group consisting of copper, and more preferably at least one metal selected from the group consisting of calcium, magnesium, zinc and lead.
- Aliphatic amides include lauric acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, oleic acid amide, eicosenoic acid amide, erucic acid amide, erucic acid amide, methylene bis stearic acid amide, ethylene bis And stearic acid amide.
- the aliphatic amide used in the present invention is preferably a fatty acid amide having 12 or more carbon atoms, more preferably a fatty acid amide having 16 to 22 carbon atoms from the viewpoint of high anti-friction properties and less mold and roll stains. An unsaturated fatty acid amide having 16 to 22 carbon atoms is more preferable.
- Examples of the fatty acid ester not having two or more hydroxyl groups in one molecule include a fatty acid ester of a monohydric alcohol, a fatty acid ester of a dihydric alcohol, and the like.
- diglyceride, triglyceride, acetylated monoglyceride examples include stearyl stearate, butyl stearate, ethylene glycol monostearate, ethylene glycol distearate and the like.
- the fatty acid ester not having two or more hydroxyl groups in one molecule used in the present invention preferably has the number of carbon atoms of the fatty acid in the fatty acid ester from the viewpoint of high anti-friction properties and less mold and roll stains. 10 or more, more preferably 16 to 24.
- the amount of the lubricant (x) is 0.001 part by mass or more and 2 parts by mass or less, preferably 0.005 part by mass or more and 1 part by mass or less, more preferably 0.001 part by mass with respect to 100 parts by mass of the copolymer (a). 01 parts by mass or more and 0.5 parts by mass or less. If the amount is less than 0.001 part by mass, the effect of the lubricant (x) is insufficient, and if the amount is more than 2 parts by mass, not only the further effect of the lubricant (x) is obtained, but these lubricants bleed out from the molded product. As a result, the surface of the molded product may become sticky.
- the lubricant (x) can be used alone or in combination of two or more. It is preferable to use a plurality of lubricants (x) having a melting point difference of 5 ° C. or more as the lubricant (x) because the effects such as anti-friction properties can be exhibited in a wider temperature range.
- the lubricant (y1) used as necessary in the resin composition according to an embodiment of the present invention is composed of a monoglyceride of a saturated fatty acid having 10 to 24 carbon atoms.
- monoglycerides of saturated fatty acids having 10 to 24 carbon atoms include monoglycerides such as glycerin monostearate and glycerin monobehenate.
- the lubricant (y2) used as necessary in the resin composition according to another embodiment of the present invention is a fatty acid ester having two or more hydroxyl groups in one molecule.
- the fatty acid ester having two or more hydroxyl groups in one molecule include polyhydric alcohol fatty acid partial esters.
- monoglycerides such as glycerin monostearate and glycerin monobehenate, pentaerythritol monostearate, penta Examples thereof include pentaerythritol mono / diester such as erythritol distearate, sorbitan mono / diester such as sorbitan monostearate, sorbitan monopalmitate, and the like.
- the fatty acid ester having two or more hydroxyl groups in one molecule preferably has 10 to 40, more preferably 10 to 24, and still more preferably 14 to 24 carbon atoms in the fatty acid.
- the fatty acid may be an unsaturated fatty acid or a saturated fatty acid.
- the amount of the lubricant (y1) or (y2) is 0.1 parts by mass or less, preferably 0.05 parts by mass or less, more preferably 0.03 parts by mass or less with respect to 100 parts by mass of the copolymer (a). More preferably, it is 0.01 parts by mass or less.
- the amount of the lubricant (y1) or (y2) is too large, a gel is generated when the resin composition is melt-molded, and there is a tendency that foreign matter defects and appearance defects are caused in the molded product.
- the resin composition of the present invention may contain various additives as necessary.
- additives include heat stabilizers, antioxidants, heat deterioration inhibitors, ultraviolet absorbers, light stabilizers, inorganic fillers, inorganic or organic fibers, polymer processing aids, antistatic agents, flame retardants, Examples thereof include dyes and pigments, colorants, matting agents, light diffusing agents, impact modifiers, phosphors, adhesives, tackifiers, plasticizers, and foaming agents.
- the content of these additives can be appropriately set as long as the effects of the present invention are not impaired.
- the content of the antioxidant is 0.01 to 1.0 part by mass
- the content of the ultraviolet absorber is 0.01 to 3.0 parts by mass
- the content is preferably 0.00001 to 0.01 parts by mass.
- the resin composition of this invention can be mixed and used for polymers other than a copolymer (a) in the range which does not impair the effect of this invention.
- examples of such other polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, Styrenic resins such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-styrene copolymer; polyester such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, polyamide elastomer Polyamide such as: Polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyace
- These other polymers may be used individually by 1 type, or may use multiple types together.
- the content of these other polymers in the resin composition of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less. .
- the method for preparing the resin composition according to the present invention is not particularly limited.
- the copolymer (a) is kneaded at a temperature equal to or higher than the softening point, and the lubricant (x) and the lubricant (y1) or the lubricant (y2) blended as necessary are blended as necessary. It can be obtained by adding an additive and another polymer and kneading, or a copolymer (a), a lubricant (x), and a lubricant (y1) or lubricant blended as necessary It can be obtained by dissolving (y2), an additive blended as necessary, and another polymer in a solvent, and removing the solvent from the solution.
- the glass transition temperature of the resin composition according to the present invention is preferably 115 ° C. or higher and 150 ° C. or lower, more preferably 130 ° C. or higher and 150 ° C. or lower, and further preferably 140 ° C. or higher and 150 ° C. or lower.
- the resin composition has a good balance of heat resistance and impact resistance.
- the high temperature and high humidity of a laminated sheet of thermoplastic resin such as the resin composition and polycarbonate can be obtained. The occurrence of warping below is suppressed.
- the resin composition according to the present invention has a saturated water absorption rate in water at 23 ° C. of preferably 0.3 to 1.8% by mass, more preferably 0.5 to 1.5% by mass, and still more preferably 0. .5 to 1.0% by mass.
- the saturated water absorption is the rate of increase in mass at the time when equilibrium is reached by immersing the molded product in distilled water at 23 ° C. and measuring the mass over time relative to the mass of the molded product vacuum-dried for 3 days or more. It is a measured value.
- the resin composition of the present invention is formed by extrusion molding methods such as co-extrusion molding, T-die lamination molding, and extrusion coating; insert injection molding, two-color injection molding, core back injection molding, sandwich injection molding, Various molded products can be obtained by heat-melt molding by an injection molding method such as an injection breath molding method; blow molding method; calendar molding method; press molding method; slush molding method.
- the resin composition of the present invention is suitable for the production of a molded product that requires high temperature molding conditions because it is difficult for a gel to form even when melt molded at a high temperature.
- the resin composition of the present invention is suitable for production of thin and wide molded articles such as sheets, films, and plates.
- the laminate of the present invention has at least one layer made of the resin composition of the present invention (hereinafter sometimes referred to as resin composition [a]) and at least one layer made of another material.
- resin composition [a] the resin composition of the present invention
- Other materials used for the laminate of the present invention are not particularly limited. Examples thereof include organic materials such as resins; inorganic materials such as simple metals and metal oxides.
- the laminate according to an embodiment of the present invention has at least one layer made of the resin composition [a] and at least one layer made of the resin composition [b].
- the resin contained in the resin composition [b] is not particularly limited.
- the resin include polyolefin such as polyethylene and polypropylene, polystyrene, (meth) acrylic resin, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyfluoride.
- the amount of polycarbonate contained in the resin composition [b] is preferably 90% by mass or more, more preferably 95% by mass or more, and 98% by mass or more. More preferably.
- the weight average molecular weight of the polycarbonate is preferably 20,000 or more and 100,000 or less. When the weight average molecular weight of the polycarbonate is within the above range, the heat resistance and impact resistance of the resin composition [b] are improved, and a laminated sheet comprising the resin composition [a] and the resin composition [b] is obtained. It can be manufactured with excellent moldability and high productivity.
- the polycarbonate has Mw / Mn of preferably 1.7 to 2.6, more preferably 1.7 to 2.3, and still more preferably 1.7 to 2.0.
- the weight average molecular weight Mw and the number average molecular weight Mn are molecular weights in terms of standard polystyrene measured by GPC (gel permeation chromatography).
- the resin composition [b] used in the present invention preferably has a glass transition temperature of 130 ° C. or higher and 160 ° C. or lower. Moreover, it is preferable that the glass transition temperature of resin composition [b] is comparable as the glass transition temperature of resin composition [a]. Specifically, the difference ⁇ Tg between the glass transition temperature of the resin composition [b] and the glass transition temperature of the resin composition [a] is preferably 30 ° C. or less, more preferably 20 ° C. or less. If the glass transition temperatures of both are the same, the effect of suppressing the occurrence of warpage of the laminated sheet under high temperature and high humidity becomes higher.
- the resin composition [b] used in the present invention may contain a known additive in order to improve heat decomposition resistance, heat discoloration resistance, light resistance and the like.
- 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 laminate according to another embodiment of the present invention includes at least one layer composed of a resin composition [a], at least one layer composed of a resin composition [b], and at least one functional layer [c]. It has.
- the functional layer [c] is not particularly limited. Examples thereof include a hard coat layer, an antistatic layer, an antifouling layer, a friction reducing layer, an antiglare layer, an antireflection layer, an adhesive layer, and an impact strength imparting layer.
- the functional layer [c] can be formed by a known method.
- the hard coat layer can be obtained by applying a resin solution for hard coat, drying and curing.
- the antireflection layer can be obtained by laminating a low refractive index film and a high refractive index film by vapor deposition or the like.
- a hard coat layer, an antistatic layer, an antifouling layer, a friction reducing layer, an antiglare layer, an antireflection layer and the like are generally provided on the outermost side of the laminate.
- functional layer [c] only 1 type may be provided and multiple types may be provided.
- the layer structure in the laminate of the present invention is not particularly limited.
- the layer made of the resin composition [a] is the [a] layer
- the layer made of the resin composition [b] is the [b] layer
- the functional layer [c] is “ For example, [a] layer / [b] layer, [a] layer / [b] layer / [a] layer, [b] layer / [a] layer / [b] layer, [c] layer, a] layer / [b] layer / [a] layer / [b] layer / [a] layer, [a] layer / [b] layer / [c] layer, [c] layer / [a] layer / [ b] layer, [c] layer / [a] layer / [b] layer, [c] layer / [a] layer / [b] layer, [c] layer / [a] layer / [b] layer / [c] layer, [c] layer / [a] layer / [b] layer / [
- [c] layer / [a] layer / [b] layer when the [c] layer is a hard coat layer, [c] layer / [a] layer / [b] layer, [c] layer / [a] layer / [b] layer / [c] layer, c) layer / [a] layer / [b] layer / [a] layer / [c] layer are preferred.
- the present invention is useful for a laminated sheet having a shape such as a sheet, a thin plate, or a film.
- the laminated sheet according to the present invention is used as a protective cover, it is preferably arranged so that the resin composition [a] layer is located on the outermost side when viewed from the surface to be protected (protected surface).
- a laminated sheet having a layer configuration of [a] layer / [b] layer is arranged in the order of [a] layer / [b] layer / protected surface, or [a] layer / [b] layer / [ It is preferable to arrange a laminated sheet having a layer configuration of a] layer in the order of [a] layer / [b] layer / [a] layer / protected surface.
- the total thickness of the laminated sheet according to the present invention is preferably 0.2 to 2 mm, more preferably 0.5 to 1.5 mm. If it is too thin, the rigidity tends to be insufficient. If it is too thick, it tends to hinder weight reduction of liquid crystal display devices.
- the thickness of the layer composed of the resin composition [a] in the laminated sheet according to the present invention is preferably in the range of 0.02 to 0.5 mm, more preferably in the range of 0.03 mm to 0.3 mm. More preferably, it is in the range of 0.05 to 0.1 mm.
- the thickness is less than 0.01 mm, scratch resistance and weather resistance may be insufficient. If it exceeds 0.5 mm, the impact resistance may be insufficient.
- the laminated sheet according to the present invention has a lamination order that is symmetrical in the thickness direction, and that the thickness of each layer is also symmetrical. More preferred.
- the laminated sheet according to the present invention is not particularly limited depending on the production method, and can be produced by a multilayer molding method such as multilayer extrusion molding, multilayer blow molding, multilayer press molding, multicolor injection molding, insert injection molding, or the like. .
- multilayer extrusion molding of the resin composition [a] and the resin composition [b] is preferable from the viewpoint of productivity.
- the method of multilayer extrusion molding is not particularly limited, and a known multilayer extrusion molding method used for manufacturing a multilayer laminated sheet of thermoplastic resin is adopted. For example, a flat T die and a polishing roll having a mirror-finished surface are provided. Molded by the machine.
- a heat-melted resin composition [a] and a resin composition [b] are laminated before the T die flows, or a resin composition [a] and a resin composition [b] ] Can be adopted such as a multi-manifold system in which T is stacked inside the T die. From the viewpoint of increasing the smoothness of the interface between the layers constituting the laminated sheet, the multi-manifold method is preferable.
- the resin composition [a] and the resin composition [b] are preferably melt filtered through a filter before multilayer molding.
- the filter used for melt filtration is not particularly limited.
- the filter is appropriately selected from known ones in terms of operating temperature, viscosity, required filtration accuracy, and the like.
- Specific examples of the filter include nonwoven fabric made of polypropylene, cotton, polyester, viscose rayon, glass fiber, etc .; phenol resin impregnated cellulose film; metal fiber nonwoven fabric sintered film; metal powder sintered film; wire mesh; Can be mentioned.
- a plurality of laminated metal fiber nonwoven fabric sintered films it is preferable to use a plurality of laminated metal fiber nonwoven fabric sintered films.
- Examples of the use of the molded article, laminate or laminated sheet according to 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 lamp cover, mood lighting cover, lamp shade, lighting parts such as light ceiling, light wall, chandelier; interior parts such as pendant and mirror; door, dome, safety window glass, partition, stair lumbar, balcony lumbar, for leisure Building parts such as roofs of buildings; aircraft windshields, pilot visors, motorcycles, motorboat windshields, bus shading plates, automotive side visors, rear visors, head wings, headlight covers, and other transportation equipment related parts; Nameplate, stereo cover, TV protective mask, vending machine Electronic equipment parts such as play covers; medical equipment parts such as incubators and X-ray parts; equipment-related parts such as machine covers, instrument covers, experimental devices, rulers, dials, and observation windows; LCD protective plates, light guide plates, and light guides Optical components such as films, Fresn
- the molded product of the present invention can be used as a front plate for various displays.
- a front plate can be obtained by a general molding method such as extrusion molding or injection molding by heating and melting the resin composition.
- the display device in which the front plate is used is not particularly limited, and examples thereof include large display devices such as large-screen televisions and advertising displays; small and medium display devices such as mobile phones and smartphones.
- the front plate is not limited to a planar shape, and may have a curved shape.
- the curved surface shape may be a shape curved in one direction or a shape curved in a plurality of directions.
- the plate-like molded body may have a flexible characteristic, or may be previously molded into a desired curved shape.
- a functional layer such as an antiglare layer, an antireflection layer, a layer that cuts electromagnetic waves, ultraviolet rays, near infrared rays, or the like may be provided.
- the molded article of the present invention may be laminated with another functional film or functional sheet via an adhesive layer or an adhesive layer, or may be laminated by film insert molding. Examples of the functional film and functional sheet include a light guide plate, a diffusion plate, a scattering prevention film, and a transparent conductive film.
- ⁇ Glass transition temperature (Tg)> In accordance with JIS K7121, the methacrylic resin or methacrylic resin composition is heated from room temperature to 200 ° C. at 20 ° C./min, held for 10 minutes, cooled to room temperature, and then from room temperature to 200 ° C. at 10 ° C. / Differential scanning calorimetry (DSC) analysis was performed under temperature conditions where the temperature was raised in minutes. The midpoint glass transition temperature obtained from the DSC curve measured at the second temperature increase was adopted as the glass transition temperature in the present invention. A DSC-50 manufactured by Shimadzu Corporation was used as a measuring device.
- DSC Differential scanning calorimetry
- ⁇ Production Example 1> In an autoclave, 63 parts by weight methyl methacrylate, 35 parts by weight tricyclo [5.2.1.0 2,6 ] dec-8-nyl methacrylate, 2 parts by weight methyl acrylate, 0.06 parts by weight Azobisisobutyronitrile, 0.01 parts by weight of 1,1-bis (t-butylperoxy) cyclohexane, 0.47 parts by weight of pentaerythritol tetrakisthiopropionate, 250 parts by weight of water, 0 0.09 parts by weight of a dispersant and 1.07 parts by weight of a pH adjuster were added.
- the liquid temperature was raised from room temperature to 70 ° C., held at 70 ° C. for 120 minutes, and then held at 120 ° C. for 60 minutes to cause a polymerization reaction.
- the liquid temperature was lowered to room temperature, and the polymerization reaction liquid was extracted from the autoclave.
- the solid content was removed from the polymerization reaction solution by filtration, washed with water, and dried in hot air at 80 ° C. for 24 hours.
- the obtained solid content was supplied to a hopper of a twin screw extruder and melt kneaded at a cylinder temperature of 230 ° C. Thereafter, the molten resin was extruded to obtain a pellet-shaped methacrylic resin [A] having a glass transition temperature of 123 ° C.
- the solid content was removed from the polymerization reaction solution by filtration, washed with water, and dried in hot air at 80 ° C. for 24 hours.
- the obtained solid content was supplied to a hopper of a twin screw extruder and melt kneaded at a cylinder temperature of 230 ° C. Thereafter, the molten resin was extruded to obtain a pellet-shaped methacrylic resin [B] having a glass transition temperature of 110 ° C.
- Example 1a 100 parts by weight of methacrylic resin [A] and 0.15 parts by weight of cetanol as a lubricant were melt-kneaded at a cylinder temperature of 230 ° C. using a biaxial kneader. Thereafter, the molten resin was extruded to obtain a pellet-shaped methacrylic resin composition [x1].
- Table 1 shows the composition and physical properties of the methacrylic resin composition [x1].
- Example 2a A methacrylic resin composition [x2] was obtained in the same manner as in Example 1a, except that 0.04 part by mass of stearic acid monoglyceride was further added as a lubricant. Table 1 shows the composition and physical properties of the methacrylic resin composition [x2].
- Example 3a A methacrylic resin composition [x3] was obtained in the same manner as in Example 1a, except that 0.1 part by mass of stearic acid monoglyceride was further added as a lubricant. Table 1 shows the composition and physical properties of the methacrylic resin composition [x3].
- Example 4a A methacrylic resin composition [x4] was obtained in the same manner as in Example 1a except that the amount of cetanol was changed to 0.3 parts by mass. Table 1 shows the composition and physical properties of the methacrylic resin composition [x4].
- Example 1a A methacrylic resin composition [x5] was obtained in the same manner as in Example 1a except that 0.15 parts by mass of cetanol was changed to 0.15 parts by mass of stearic acid monoglyceride. Table 1 shows the composition and physical properties of the methacrylic resin composition [x5].
- the resin compositions according to the present invention (Examples 1a to 4a) have a high glass transition temperature and low water absorption.
- ⁇ Appearance> The number of foreign material defects was counted by visually observing the methacrylic resin side surface of the laminated sheet. Within the area of 1 m 2 , the number of defects was 1 or less, ⁇ , 2 was ⁇ , 3 was ⁇ , 4 or more was x. .
- ⁇ Moldability> The surface of the laminated sheet on the methacrylic resin side was visually observed to inspect for the presence or absence of step-like defects (release marks) perpendicular to the extrusion flow direction. In the range of 30 cm in the extrusion flow direction, ⁇ indicates that the stepped defect was not visible at all, ⁇ indicates that it was hardly visible, ⁇ indicates that it was slightly visible, and ⁇ indicates that it was clearly visible. .
- ⁇ War change amount> A rectangular test piece having a short side of 30 mm and a long side of 150 mm was cut out from the laminated sheet so that the direction perpendicular to the extrusion flow direction was the short side and the direction parallel to the extrusion flow direction was the long side.
- the short side of the test piece was picked and hung and left in an environmental test machine set at a temperature of 23 ° C. and a relative humidity of 50% for 72 hours.
- the test piece was allowed to cool to 23 ° C.
- the test piece Place the test piece warped in a bow shape on the surface plate so that the end of the test piece is in contact with the surface plate (that is, the test piece is chevron-shaped), and the gap between the surface plate and the test piece is The maximum distance (usually, the vicinity of the center of the long side of the test piece is maximum) was measured using a gap gauge. This value was used as the initial warpage amount. Subsequently, the short side of the bowed test piece was picked and hung and left in an environmental test machine set at a temperature of 85 ° C. and a relative humidity of 85% for 24 hours. The test piece was allowed to cool to 23 ° C. The maximum distance of the gap between the surface plate and the test piece was measured by the same method as above.
- warpage change amount The difference between this measured value and the initial warpage amount was defined as “warpage change amount”.
- a curve having a warpage variation of 1 mm or less was marked with ⁇ , and a curve having a curvature variation of more than 1 mm was marked with ⁇ .
- Example 1b Pellets of polycarbonate (“SD Polycarbonate (registered trademark) PCX” manufactured by Sumika Stylon Polycarbonate Co., Ltd., hereinafter the same)) are placed on a single screw extruder [I] with a shaft diameter of 50 mm set at a cylinder temperature of 280 ° C. and a discharge rate of 30 kg / hour. Were continuously charged. Pellets of the methacrylic resin composition [x1] were continuously charged into a single screw extruder [II] having a shaft diameter of 30 mm and set at a cylinder temperature of 220 ° C. and a discharge rate of 2 kg / hour.
- SD Polycarbonate (registered trademark) PCX manufactured by Sumika Stylon Polycarbonate Co., Ltd., hereinafter the same
- the polycarbonate and the methacrylic resin composition [x1] are simultaneously extruded from the extruder [I] and the extruder [II], introduced into the junction block, and then the polycarbonate and the methacrylic resin composition [x1] with a multi-manifold die having a temperature of 250 ° C. Were coextruded to form a sheet.
- the sheet was formed into a bank between No. 1 and No. 2 rolls of four horizontal rolls, cooled while transferring the mirror surface with the four rolls, and a layer and a thickness of the methacrylic resin composition [x1] having a thickness of 60 ⁇ m.
- a laminated sheet having a total thickness of 1000 ⁇ m consisting of a polycarbonate layer having a thickness of 940 ⁇ m was obtained.
- the evaluation results of the laminated sheet are shown in Table 2.
- Example 2b A layer composed of a methacrylic resin composition [x2] having a thickness of 60 ⁇ m and a polycarbonate having a thickness of 940 ⁇ m were prepared in the same manner as in Example 1b except that the methacrylic resin composition [x1] was changed to a methacrylic resin composition [x2]. A laminated sheet having a total thickness of 1000 ⁇ m was obtained. The evaluation results of the laminated sheet are shown in Table 2.
- Example 3b A layer composed of a methacrylic resin composition [x3] having a thickness of 60 ⁇ m and a polycarbonate having a thickness of 940 ⁇ m were prepared in the same manner as in Example 1b except that the methacrylic resin composition [x1] was changed to a methacrylic resin composition [x3]. A laminated sheet having a total thickness of 1000 ⁇ m was obtained. The evaluation results of the laminated sheet are shown in Table 2.
- Example 4b Except for changing the methacrylic resin composition [x1] to the methacrylic resin composition [x4], a layer composed of the methacrylic resin composition [x4] having a thickness of 60 ⁇ m and a polycarbonate having a thickness of 940 ⁇ m were prepared in the same manner as in Example 1b. A laminated sheet having a total thickness of 1000 ⁇ m was obtained. The evaluation results of the laminated sheet are shown in Table 2.
- Example 1b A layer composed of a methacrylic resin composition [x5] having a thickness of 60 ⁇ m and a polycarbonate having a thickness of 940 ⁇ m were prepared in the same manner as in Example 1b except that the methacrylic resin composition [x1] was changed to a methacrylic resin composition [x5]. A laminated sheet having a total thickness of 1000 ⁇ m was obtained. The evaluation results of the laminated sheet are shown in Table 2.
- ⁇ Comparative Example 2b> A layer composed of a methacrylic resin composition [x6] having a thickness of 60 ⁇ m and a polycarbonate having a thickness of 940 ⁇ m were prepared in the same manner as in Example 1b except that the methacrylic resin composition [x1] was changed to a methacrylic resin composition [x6]. A laminated sheet having a total thickness of 1000 ⁇ m was obtained. The evaluation results of the laminated sheet are shown in Table 2.
- Example 3b A layer composed of a methacrylic resin composition [x7] having a thickness of 60 ⁇ m and a polycarbonate having a thickness of 940 ⁇ m were prepared in the same manner as in Example 1b except that the methacrylic resin composition [x1] was changed to a methacrylic resin composition [x7]. A laminated sheet having a total thickness of 1000 ⁇ m was obtained. The evaluation results of the laminated sheet are shown in Table 2.
- the laminates according to the present invention (Examples 1b to 4b) have few foreign matter defects due to gels and the like that may be generated during melt molding, and few release marks. Furthermore, the laminated body according to the present invention is less warped even when left under high temperature and high humidity.
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Abstract
Description
本発明の課題は、溶融成形時にゲルが生成し難い、耐熱性に優れた樹脂組成物およびその成形品を提供することである。 When a methacrylic resin composition with improved heat resistance is mixed with a lubricant and melt-molded, a gel may be formed. This gel becomes a foreign matter defect of the molded product, or the appearance of the product is impaired.
An object of the present invention is to provide a resin composition that hardly forms a gel during melt molding and has excellent heat resistance, and a molded product thereof.
高級アルコール、炭化水素、脂肪酸、脂肪酸金属塩、脂肪族アミド、および1分子中に水酸基を2以上有しない脂肪酸エステルからなる群より選ばれる少なくとも一つからなる滑剤(x)0.001質量部以上2質量部以下と、
炭素原子数10~24の飽和脂肪酸のモノグリセライドからなる滑剤(y1)0~0.1質量部と
を含有する樹脂組成物。 [1] 100 parts by mass of a copolymer (a) composed of a structural unit derived from a methacrylic acid alicyclic hydrocarbon ester and a structural unit derived from another monomer;
Lubricant (x) consisting of at least one selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters having no two or more hydroxyl groups in one molecule (x) 0.001 parts by mass or more 2 parts by mass or less,
A resin composition comprising 0 to 0.1 parts by mass of a lubricant (y1) comprising a monoglyceride of a saturated fatty acid having 10 to 24 carbon atoms.
〔3〕 滑剤(y1)の含有量が、共重合体(a)100質量部に対して0~0.01質量部である〔1〕に記載の樹脂組成物。 [2] The resin composition according to [1], wherein the content of the lubricant (y1) is 0 to 0.05 parts by mass with respect to 100 parts by mass of the copolymer (a).
[3] The resin composition according to [1], wherein the content of the lubricant (y1) is 0 to 0.01 parts by mass with respect to 100 parts by mass of the copolymer (a).
高級アルコール、炭化水素、脂肪酸、脂肪酸金属塩、脂肪族アミド、および1分子中に水酸基を2以上有しない脂肪酸エステルからなる群より選ばれる少なくとも一つからなる滑剤(x)0.001質量部以上2質量部以下と、
1分子中に水酸基を2以上有する脂肪酸エステルからなる滑剤(y2)0~0.1質量部と
を含有する樹脂組成物。 [4] 100 parts by mass of a copolymer (a) composed of a structural unit derived from a methacrylic acid alicyclic hydrocarbon ester and a structural unit derived from another monomer;
Lubricant (x) consisting of at least one selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters having no two or more hydroxyl groups in one molecule (x) 0.001 parts by mass or more 2 parts by mass or less,
A resin composition comprising 0 to 0.1 parts by mass of a lubricant (y2) comprising a fatty acid ester having two or more hydroxyl groups in one molecule.
〔6〕 滑剤(y2)の含有量が、共重合体(a)100質量部に対して0~0.01質量部である〔4〕に記載の樹脂組成物。 [5] The resin composition according to [4], wherein the content of the lubricant (y2) is 0 to 0.05 parts by mass with respect to 100 parts by mass of the copolymer (a).
[6] The resin composition according to [4], wherein the content of the lubricant (y2) is 0 to 0.01 part by mass with respect to 100 parts by mass of the copolymer (a).
〔8〕 ガラス転移温度が115℃以上150℃以下である〔1〕~〔7〕のいずれかひとつに記載の樹脂組成物。
〔9〕 23℃の水中における飽和吸水率が0.3~1.8質量%である〔1〕~〔8〕のいずれかひとつに記載の樹脂組成物。 [7] The lubricant (x) comprises at least one selected from the group consisting of aliphatic monohydric alcohols having 12 to 18 carbon atoms and saturated fatty acids having 16 to 24 carbon atoms. 6]. The resin composition according to any one of [6].
[8] The resin composition according to any one of [1] to [7], which has a glass transition temperature of 115 ° C. or higher and 150 ° C. or lower.
[9] The resin composition according to any one of [1] to [8], wherein a saturated water absorption in water at 23 ° C. is 0.3 to 1.8% by mass.
〔11〕 前記〔1〕~〔9〕のいずれかひとつに記載の樹脂組成物からなる層と、
ガラス転移温度が130℃以上160℃以下である熱可塑性樹脂組成物からなる層とを有する積層体。
〔12〕 ガラス転移温度が130℃以上160℃以下である熱可塑性樹脂組成物がポリカーボネートを含有する樹脂組成物である〔11〕に記載の積層体。 [10] A molded product comprising the resin composition according to any one of [1] to [9].
[11] A layer formed of the resin composition according to any one of [1] to [9],
And a layer made of a thermoplastic resin composition having a glass transition temperature of 130 ° C. or higher and 160 ° C. or lower.
[12] The laminate according to [11], wherein the thermoplastic resin composition having a glass transition temperature of 130 ° C. or higher and 160 ° C. or lower is a resin composition containing polycarbonate.
また、メタクリル酸脂環式炭化水素エステルおよびメタクリル酸メチル以外の単量体に由来する構造単位の含有率は、好ましくは10質量%以下、より好ましくは5質量%以下、さらに好ましくは2質量%以下である。 In the copolymer (a) suitably used in the present invention, the content of structural units derived from methyl methacrylate is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and still more preferably 60 to 70% by mass. If the content of the structural unit derived from methyl methacrylate is less than the above range, the transparency, scratch resistance and weather resistance of the resin composition may be inferior. When the content rate of the structural unit derived from methyl methacrylate is more than the above range, the heat resistance of the resin composition may be inferior.
The content of structural units derived from monomers other than methacrylic acid alicyclic hydrocarbon ester and methyl methacrylate is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass. It is as follows.
なお、重量平均分子量および数平均分子量は、GPC(ゲルパーミエーションクロマトグラフィ)で測定した標準ポリスチレン換算の分子量である。
また、共重合体(a)の重量平均分子量、数平均分子量およびMw/Mnは、後述する重合開始剤および連鎖移動剤の種類や量などを調整することによって制御できる。 In the copolymer (a) used in the present invention, the ratio of the weight average molecular weight to the number average molecular weight (sometimes referred to as Mw / Mn) is preferably 1.7 or more and 2.6 or less, more preferably It is 1.7 or more and 2.3 or less, More preferably, it is 1.7 or more and 2.0 or less.
In addition, 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 weight average molecular weight, number average molecular weight, and Mw / Mn of the copolymer (a) can be controlled by adjusting the types and amounts of the polymerization initiator and chain transfer agent described later.
重合反応は単量体混合物とともに添加した重合開始剤によって開始される。また、必要に応じて連鎖移動剤を単量体混合物に添加することによって、得られる共重合体(a)の重量平均分子量、数平均分子量、分子量分布を調節できる。 The production of the copolymer (a) used in the present invention is not particularly limited by the polymerization method. Examples include suspension polymerization, (continuous) bulk polymerization, solution polymerization, and emulsion polymerization. The polymerization method is preferably performed by radical polymerization. Of these polymerization methods, the suspension polymerization method or the (continuous) bulk polymerization method is preferable, and the suspension polymerization method is more preferable from the viewpoints of productivity and thermal decomposition resistance.
The polymerization reaction is initiated by a polymerization initiator added with the monomer mixture. Moreover, the weight average molecular weight of the copolymer (a) obtained, a number average molecular weight, and molecular weight distribution can be adjusted by adding a chain transfer agent to a monomer mixture as needed.
これらのうち、本発明に用いられる滑剤(x)は、高級アルコール、炭化水素、脂肪酸、脂肪酸金属塩、脂肪族アミド、および1分子中に水酸基を2以上有しない脂肪酸エステルからなる群より選ばれる少なくとも一つからなるもの、好ましくは炭素原子数12~18の脂肪族1価アルコールおよび炭素原子数16~24の飽和脂肪酸からなる群より選ばれる少なくとも一つからなるもの、より好ましくは炭素原子数12~18の脂肪族1価アルコールからなるものである。 The lubricant is a known additive that is added to the resin in order to impart lubricity and releasability. Known lubricants include higher alcohol lubricants, hydrocarbon lubricants, fatty acid lubricants, fatty acid metal salt lubricants, aliphatic amide lubricants, ester lubricants, and the like.
Among these, the lubricant (x) used in the present invention is selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters having no two or more hydroxyl groups in one molecule. At least one, preferably at least one selected from the group consisting of aliphatic monohydric alcohols having 12 to 18 carbon atoms and saturated fatty acids having 16 to 24 carbon atoms, more preferably the number of carbon atoms It consists of 12-18 aliphatic monohydric alcohols.
脂肪酸金属塩を構成する脂肪酸としては、減摩性が高く且つ金型汚れやロール汚れが少ないという観点から、炭素原子数10以上の脂肪酸が好ましく、炭素原子数16~24の脂肪酸がより好ましく、炭素原子数16~24の飽和脂肪酸がさらに好ましい。脂肪酸金属塩を構成する金属としては、安定性、減摩性の観点から、カルシウム、マグネシウム、亜鉛、鉛、錫、鉄、カドミウム、アルミニウム、バリウム、コバルト、ニッケル、マンガン、ストロンチウム、チタン、バナジウム、および銅からなる群より選ばれる少なくとも1つの金属を含むことが好ましく、カルシウム、マグネシウム、亜鉛および鉛からなる群より選ばれる少なくとも1つの金属を含むことがより好ましい。 Examples of fatty acid metal salts include cadmium stearate, cadmium laurate, cadmium ricinoleate, cadmium naphthenate, cadmium 2-ethylhexoate, barium stearate, barium laurate, barium ricinoleate, barium naphthenate, barium 2-ethylhexoate, Calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate, zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexoate, lead stearate, dibasic lead stearate, lead naphthenate, tin stearate , Aluminum stearate, magnesium stearate and the like.
The fatty acid constituting the fatty acid metal salt is preferably a fatty acid having 10 or more carbon atoms, more preferably a fatty acid having 16 to 24 carbon atoms, from the viewpoint of high anti-friction properties and less mold dirt and roll dirt. More preferred are saturated fatty acids having 16 to 24 carbon atoms. As the metal constituting the fatty acid metal salt, calcium, magnesium, zinc, lead, tin, iron, cadmium, aluminum, barium, cobalt, nickel, manganese, strontium, titanium, vanadium, from the viewpoint of stability and antifriction And at least one metal selected from the group consisting of copper, and more preferably at least one metal selected from the group consisting of calcium, magnesium, zinc and lead.
本発明の樹脂組成物中における、これら他の重合体の含有量は、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、2質量%以下であることがさらに好ましい。 Moreover, the resin composition of this invention can be mixed and used for polymers other than a copolymer (a) in the range which does not impair the effect of this invention. Examples of such other polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, Styrenic resins such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-styrene copolymer; polyester such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, polyamide elastomer Polyamide such as: Polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurea Emissions, modified polyphenylene ether, polyphenylene sulfide, silicone-modified resins; can be mentioned IR, EPR, and olefin rubbers such as EPDM; acrylic rubber, silicone rubber; SEPS, SEBS, styrene-based thermoplastic elastomers such as SIS. These other polymers may be used individually by 1 type, or may use multiple types together.
The content of these other polymers in the resin composition of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less. .
多層押出し成形の方法は特に限定されず、熱可塑性樹脂の多層積層シートの製造に用いられる公知の多層押出し成形法が採用され、例えば、フラットなTダイと表面が鏡面仕上げされたポリシングロールを備えた装置によって成形される。Tダイの方式としては、加熱溶融状態の樹脂組成物[a]および樹脂組成物[b]がTダイ流入前に積層されるフィードブロック方式、あるいは樹脂組成物[a]および樹脂組成物[b]がTダイ内部で積層されるマルチマニホールド方式などを採用できる。積層シートを構成する各層間の界面の平滑性を高める観点から、マルチマニホールド方式が好ましい。 The laminated sheet according to the present invention is not particularly limited depending on the production method, and can be produced by a multilayer molding method such as multilayer extrusion molding, multilayer blow molding, multilayer press molding, multicolor injection molding, insert injection molding, or the like. . Among these multilayer molding methods, multilayer extrusion molding of the resin composition [a] and the resin composition [b] is preferable from the viewpoint of productivity.
The method of multilayer extrusion molding is not particularly limited, and a known multilayer extrusion molding method used for manufacturing a multilayer laminated sheet of thermoplastic resin is adopted. For example, a flat T die and a polishing roll having a mirror-finished surface are provided. Molded by the machine. As a method of the T die, a heat-melted resin composition [a] and a resin composition [b] are laminated before the T die flows, or a resin composition [a] and a resin composition [b] ] Can be adopted such as a multi-manifold system in which T is stacked inside the T die. From the viewpoint of increasing the smoothness of the interface between the layers constituting the laminated sheet, the multi-manifold method is preferable.
前記フィルターの濾過精度に特に制限はないが、30μm以下であることが好ましく、10μm以下であることがより好ましく、5μm以下であることがさらに好ましい。 The resin composition [a] and the resin composition [b] are preferably melt filtered through a filter before multilayer molding. By performing multilayer molding using each melt-filtered resin composition, a laminated sheet with few defects due to foreign matters, gels and the like can be obtained. The filter used for melt filtration is not particularly limited. The filter is appropriately selected from known ones in terms of operating temperature, viscosity, required filtration accuracy, and the like. Specific examples of the filter include nonwoven fabric made of polypropylene, cotton, polyester, viscose rayon, glass fiber, etc .; phenol resin impregnated cellulose film; metal fiber nonwoven fabric sintered film; metal powder sintered film; wire mesh; Can be mentioned. Among these, from the viewpoint of heat resistance, durability and pressure resistance, it is preferable to use a plurality of laminated metal fiber nonwoven fabric sintered films.
Although there is no restriction | limiting in particular in the filtration precision of the said filter, It is preferable that it is 30 micrometers or less, It is more preferable that it is 10 micrometers or less, It is further more preferable that it is 5 micrometers or less.
前記前面板が用いられるディスプレイ装置は、特に限定されず、例えば、大画面テレビや広告用ディスプレイなどの大型ディスプレイ装置;携帯電話やスマートフォンのような中小型ディスプレイ装置などが挙げられる。
前記前面板は、平面状に限られず曲面形状を有しても良い。前記曲面形状は一方向に湾曲した形状であってもよいし、複数の方向に湾曲した形状であっても良い。前記前面板を曲面形状とするために、前記板状成形体は、フレキシブル特性を有してもよいし、予め所望の曲面形状に成形されていてもよい。 The molded product of the present invention can be used as a front plate for various displays. Such a front plate can be obtained by a general molding method such as extrusion molding or injection molding by heating and melting the resin composition.
The display device in which the front plate is used is not particularly limited, and examples thereof include large display devices such as large-screen televisions and advertising displays; small and medium display devices such as mobile phones and smartphones.
The front plate is not limited to a planar shape, and may have a curved shape. The curved surface shape may be a shape curved in one direction or a shape curved in a plurality of directions. In order to make the front plate have a curved shape, the plate-like molded body may have a flexible characteristic, or may be previously molded into a desired curved shape.
本発明の成形品は、他の機能フィルムや機能シートと接着層や粘着層を介して積層してもよく、フィルムインサート成形により積層してもよい。前記機能フィルムや機能シートとしては、導光板や拡散板、飛散防止フィルム、透明導電フィルムなどが挙げられる。 Moreover, you may use the molded article of this invention for the above-mentioned various uses in the state hard-coated by methods, such as spray coating and dip coating, on the surface. Hard coating increases the pencil hardness of the surface and makes it difficult to scratch. In addition to the hard coat, a functional layer such as an antiglare layer, an antireflection layer, a layer that cuts electromagnetic waves, ultraviolet rays, near infrared rays, or the like may be provided.
The molded article of the present invention may be laminated with another functional film or functional sheet via an adhesive layer or an adhesive layer, or may be laminated by film insert molding. Examples of the functional film and functional sheet include a light guide plate, a diffusion plate, a scattering prevention film, and a transparent conductive film.
JIS K7121に準拠して、メタクリル樹脂またはメタクリル樹脂組成物を、室温から200℃まで20℃/分で昇温し、10分間保持し、室温まで冷却し、次いで室温から200℃までを10℃/分で昇温させる温度条件において示差走査熱量(DSC)分析を行った。2回目の昇温時に測定されるDSC曲線から求められる中間点ガラス転移温度を本発明におけるガラス転移温度として採用した。測定装置として島津製作所製DSC-50を用いた。 <Glass transition temperature (Tg)>
In accordance with JIS K7121, the methacrylic resin or methacrylic resin composition is heated from room temperature to 200 ° C. at 20 ° C./min, held for 10 minutes, cooled to room temperature, and then from room temperature to 200 ° C. at 10 ° C. / Differential scanning calorimetry (DSC) analysis was performed under temperature conditions where the temperature was raised in minutes. The midpoint glass transition temperature obtained from the DSC curve measured at the second temperature increase was adopted as the glass transition temperature in the present invention. A DSC-50 manufactured by Shimadzu Corporation was used as a measuring device.
射出成形機(住友重機械工業株式会社製、SE-180DU-HP)を用いて、シリンダ温度280℃、金型温度75℃および成形サイクル1分の条件でメタクリル樹脂組成物を射出成形して、厚さ2mm、一辺50mmの正方形の試験片を得た。温度80℃、5mmHgの条件下において試験片を24時間真空乾燥させた。次いで、試験片をデシケータ中で放冷した。デシケータから試験片を取り出して直ぐに質量(初期質量)を測定した。
次いで該試験片を23℃の蒸留水に浸漬した。試験片を水から取り出し、表面に付着した水を拭き取って質量を測定した。該試験片を蒸留水に浸漬し、上記と同様にして質量を測定した。質量変化がなくなるまで蒸留水への浸漬、質量測定を繰り返した。質量変化がなくなったときの質量(吸水質量)と、初期質量とから、下式によって飽和吸水率を算出した。
飽和吸水率(%)=[(吸水質量-初期質量)/初期質量]×100 <Saturated water absorption>
Using an injection molding machine (SE-180DU-HP, manufactured by Sumitomo Heavy Industries, Ltd.), a methacrylic resin composition was injection molded under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 75 ° C. and a molding cycle of 1 minute, A square test piece having a thickness of 2 mm and a side of 50 mm was obtained. The test piece was vacuum-dried for 24 hours under the conditions of a temperature of 80 ° C. and 5 mmHg. The test piece was then allowed to cool in a desiccator. Immediately after removing the test piece from the desiccator, the mass (initial mass) was measured.
Subsequently, this test piece was immersed in 23 degreeC distilled water. The test piece was taken out of the water, the water adhering to the surface was wiped off, and the mass was measured. The test piece was immersed in distilled water, and the mass was measured in the same manner as described above. Immersion in distilled water and mass measurement were repeated until there was no change in mass. A saturated water absorption rate was calculated from the mass (water absorption mass) when the mass change disappeared and the initial mass by the following equation.
Saturated water absorption (%) = [(water absorption−initial mass) / initial mass] × 100
オートクレーブに、63質量部のメタクリル酸メチル、35質量部のメタクリル酸トリシクロ[5.2.1.02,6]デカ-8-ニル、2質量部のアクリル酸メチル、0.06質量部のアゾビスイソブチロニトリル、0.01質量部の1,1-ビス(t-ブチルパーオキシ)シクロへキサン、0.47質量部のペンタエリスリトールテトラキスチオプロピオネート、250質量部の水、0.09質量部の分散剤および1.07質量部のpH調整剤を入れた。 <Production Example 1>
In an autoclave, 63 parts by weight methyl methacrylate, 35 parts by weight tricyclo [5.2.1.0 2,6 ] dec-8-nyl methacrylate, 2 parts by weight methyl acrylate, 0.06 parts by weight Azobisisobutyronitrile, 0.01 parts by weight of 1,1-bis (t-butylperoxy) cyclohexane, 0.47 parts by weight of pentaerythritol tetrakisthiopropionate, 250 parts by weight of water, 0 0.09 parts by weight of a dispersant and 1.07 parts by weight of a pH adjuster were added.
オートクレーブに、96.5質量部のメタクリル酸メチル、2.5質量部のアクリル酸メチル、0.06質量部のアゾビスイソブチロニトリル、0.25質量部のn-オクチルメルカプタン、250質量部の水、0.09質量部の分散剤および1.07質量部のpH調整剤を入れた。
オートクレーブ内を攪拌しながら、液温を室温から70℃に上げ、70℃で120分間保持して、重合反応を行った。液温を室温まで下げ、重合反応液をオートクレーブから抜き出した。重合反応液から固形分を濾過で取り出し、水で洗浄し、80℃にて24時間熱風乾燥させた。得られた固形分を2軸押出機のホッパーに供給し、シリンダ温度230℃で溶融混練した。その後、溶融樹脂を押し出して、ガラス転移温度110℃のペレット状のメタクリル樹脂[B]を得た。 <Production Example 2>
In an autoclave, 96.5 parts by mass of methyl methacrylate, 2.5 parts by mass of methyl acrylate, 0.06 parts by mass of azobisisobutyronitrile, 0.25 parts by mass of n-octyl mercaptan, 250 parts by mass Of water, 0.09 parts by weight of dispersant and 1.07 parts by weight of pH adjuster were added.
While stirring the inside of the autoclave, the liquid temperature was raised from room temperature to 70 ° C. and held at 70 ° C. for 120 minutes to carry out the polymerization reaction. The liquid temperature was lowered to room temperature, and the polymerization reaction liquid was extracted from the autoclave. The solid content was removed from the polymerization reaction solution by filtration, washed with water, and dried in hot air at 80 ° C. for 24 hours. The obtained solid content was supplied to a hopper of a twin screw extruder and melt kneaded at a cylinder temperature of 230 ° C. Thereafter, the molten resin was extruded to obtain a pellet-shaped methacrylic resin [B] having a glass transition temperature of 110 ° C.
メタクリル樹脂[A]100質量部および滑剤としてセタノール0.15質量部を2軸混練機にてシリンダ温度230℃で溶融混練した。その後、溶融樹脂を押し出して、ペレット状のメタクリル樹脂組成物[x1]を得た。メタクリル樹脂組成物[x1]の組成および物性を表1に示す。 <Example 1a>
100 parts by weight of methacrylic resin [A] and 0.15 parts by weight of cetanol as a lubricant were melt-kneaded at a cylinder temperature of 230 ° C. using a biaxial kneader. Thereafter, the molten resin was extruded to obtain a pellet-shaped methacrylic resin composition [x1]. Table 1 shows the composition and physical properties of the methacrylic resin composition [x1].
滑剤としてステアリン酸モノグリセライド0.04質量部をさらに加えた以外は、実施例1aと同じ手法にてメタクリル樹脂組成物[x2]を得た。メタクリル樹脂組成物[x2]の組成および物性を表1に示す。 <Example 2a>
A methacrylic resin composition [x2] was obtained in the same manner as in Example 1a, except that 0.04 part by mass of stearic acid monoglyceride was further added as a lubricant. Table 1 shows the composition and physical properties of the methacrylic resin composition [x2].
滑剤としてステアリン酸モノグリセライド0.1質量部をさらに加えた以外は、、実施例1aと同じ手法にてメタクリル樹脂組成物[x3]を得た。メタクリル樹脂組成物[x3]の組成および物性を表1に示す。 <Example 3a>
A methacrylic resin composition [x3] was obtained in the same manner as in Example 1a, except that 0.1 part by mass of stearic acid monoglyceride was further added as a lubricant. Table 1 shows the composition and physical properties of the methacrylic resin composition [x3].
セタノールの量を0.3質量部に変えた以外は、実施例1aと同じ方法にてメタクリル樹脂組成物[x4]を得た。メタクリル樹脂組成物[x4]の組成および物性を表1に示す。 <Example 4a>
A methacrylic resin composition [x4] was obtained in the same manner as in Example 1a except that the amount of cetanol was changed to 0.3 parts by mass. Table 1 shows the composition and physical properties of the methacrylic resin composition [x4].
セタノール0.15質量部をステアリン酸モノグリセライド0.15質量部に変えた以外は、実施例1aと同じ方法にてメタクリル樹脂組成物[x5]を得た。メタクリル樹脂組成物[x5]の組成および物性を表1に示す。 <Comparative Example 1a>
A methacrylic resin composition [x5] was obtained in the same manner as in Example 1a except that 0.15 parts by mass of cetanol was changed to 0.15 parts by mass of stearic acid monoglyceride. Table 1 shows the composition and physical properties of the methacrylic resin composition [x5].
滑剤としてセタノール0.15質量部をさらに加えた以外は、比較例1aと同じ手法にてメタクリル樹脂組成物[x6]を得た。メタクリル樹脂組成物[x6]の組成および物性を表1に示す。 <Comparative Example 2a>
A methacrylic resin composition [x6] was obtained in the same manner as in Comparative Example 1a except that 0.15 parts by mass of cetanol was further added as a lubricant. Table 1 shows the composition and physical properties of the methacrylic resin composition [x6].
メタクリル樹脂[A]をメタクリル樹脂[B]に変えた以外は、比較例1aと同じ方法にてペレット状のメタクリル樹脂組成物[x7]を得た。メタクリル樹脂組成物[x7]の組成および物性を表1に示す。 <Comparative Example 3a>
A pellet-shaped methacrylic resin composition [x7] was obtained in the same manner as in Comparative Example 1a except that the methacrylic resin [A] was changed to the methacrylic resin [B]. Table 1 shows the composition and physical properties of the methacrylic resin composition [x7].
積層シートのメタクリル樹脂側表面を目視観察して異物欠点の数を数えた。
1m2の面積内において、欠点の数が1個以下であったものを◎、2個であったものを○、3個であったものを△、4個以上であったものを×とした。 <Appearance>
The number of foreign material defects was counted by visually observing the methacrylic resin side surface of the laminated sheet.
Within the area of 1 m 2 , the number of defects was 1 or less, ◎, 2 was ◯, 3 was △, 4 or more was x. .
積層シートのメタクリル樹脂側表面を目視観察して押出流れ方向に直交する段差状欠点(離型マーク)の有無を検査した。
押出流れ方向に30cmの範囲において、段差状欠点が全く視認できなかったものを◎、ほとんど視認できなかったものを○、わずかに視認できたものを△、明瞭に視認できたものを×とした。 <Moldability>
The surface of the laminated sheet on the methacrylic resin side was visually observed to inspect for the presence or absence of step-like defects (release marks) perpendicular to the extrusion flow direction.
In the range of 30 cm in the extrusion flow direction, ◎ indicates that the stepped defect was not visible at all, ○ indicates that it was hardly visible, △ indicates that it was slightly visible, and × indicates that it was clearly visible. .
積層シートから、押出流れ方向に対して垂直な方向が短辺、押出流れ方向に対して平行な方向が長辺となるように、短辺30mm、長辺150mmの長方形試験片を切り出した。試験片の短辺を摘み吊り、温度23℃、相対湿度50%に設定した環境試験機の中に、72時間放置した。試験片を23℃に放冷した。試験片は弓状に反った。弓状に反った試験片を、定盤の上に該試験片を端部が定盤に接するように(すなわち、試験片が山形になるように)置き、定盤と試験片との隙間の最大距離(通常、試験片の長辺中央部付近が最大となる。)を、隙間ゲージを用いて測定した。この値を初期反り量とした。
続いて、弓状に反った試験片の短辺を摘み吊り、温度85℃、相対湿度85%に設定した環境試験機の中に、24時間放置した。試験片を23℃に放冷した。上記と同じ方法で定盤と試験片との隙間の最大距離を測定した。この測定値と初期反り量との差を「反り変化量」と定義した。反り変化量が1mm以下のものを◎、反り変化量が1mm超のものを×とした。 <War change amount>
A rectangular test piece having a short side of 30 mm and a long side of 150 mm was cut out from the laminated sheet so that the direction perpendicular to the extrusion flow direction was the short side and the direction parallel to the extrusion flow direction was the long side. The short side of the test piece was picked and hung and left in an environmental test machine set at a temperature of 23 ° C. and a relative humidity of 50% for 72 hours. The test piece was allowed to cool to 23 ° C. The specimen warped in an arc. Place the test piece warped in a bow shape on the surface plate so that the end of the test piece is in contact with the surface plate (that is, the test piece is chevron-shaped), and the gap between the surface plate and the test piece is The maximum distance (usually, the vicinity of the center of the long side of the test piece is maximum) was measured using a gap gauge. This value was used as the initial warpage amount.
Subsequently, the short side of the bowed test piece was picked and hung and left in an environmental test machine set at a temperature of 85 ° C. and a relative humidity of 85% for 24 hours. The test piece was allowed to cool to 23 ° C. The maximum distance of the gap between the surface plate and the test piece was measured by the same method as above. The difference between this measured value and the initial warpage amount was defined as “warpage change amount”. A curve having a warpage variation of 1 mm or less was marked with ◎, and a curve having a curvature variation of more than 1 mm was marked with ×.
シリンダ温度280℃、吐出量30kg/時に設定された、軸径50mmの単軸押出機[I]にポリカーボネート(住化スタイロンポリカーボネート株式会社製「SDポリカ(登録商標)PCX」。以下同じ)のペレットを連続的に投入した。
シリンダ温度220℃、吐出量2kg/時に設定された、軸径30mmの単軸押出機[II]にメタクリル樹脂組成物[x1]のペレットを連続的に投入した。
押出機[I]および押出機[II]から同時にポリカーボネートとメタクリル樹脂組成物[x1]とを押出して、ジャンクションブロックに導入し、次いで温度250℃のマルチマニホールドダイでポリカーボネートとメタクリル樹脂組成物[x1]とを共押出成形してシート状にした。このシートを、横4本ロールの1,2番ロール間にてバンク成形し、4本ロールにて鏡面を転写しながら冷却し、厚さ60μmのメタクリル樹脂組成物[x1]からなる層と厚さ940μmのポリカーボネートからなる層とからなる総厚さ1000μmの積層シートを得た。積層シートの評価結果を表2に示す。 <Example 1b>
Pellets of polycarbonate (“SD Polycarbonate (registered trademark) PCX” manufactured by Sumika Stylon Polycarbonate Co., Ltd., hereinafter the same)) are placed on a single screw extruder [I] with a shaft diameter of 50 mm set at a cylinder temperature of 280 ° C. and a discharge rate of 30 kg / hour. Were continuously charged.
Pellets of the methacrylic resin composition [x1] were continuously charged into a single screw extruder [II] having a shaft diameter of 30 mm and set at a cylinder temperature of 220 ° C. and a discharge rate of 2 kg / hour.
The polycarbonate and the methacrylic resin composition [x1] are simultaneously extruded from the extruder [I] and the extruder [II], introduced into the junction block, and then the polycarbonate and the methacrylic resin composition [x1] with a multi-manifold die having a temperature of 250 ° C. Were coextruded to form a sheet. The sheet was formed into a bank between No. 1 and No. 2 rolls of four horizontal rolls, cooled while transferring the mirror surface with the four rolls, and a layer and a thickness of the methacrylic resin composition [x1] having a thickness of 60 μm. A laminated sheet having a total thickness of 1000 μm consisting of a polycarbonate layer having a thickness of 940 μm was obtained. The evaluation results of the laminated sheet are shown in Table 2.
メタクリル樹脂組成物[x1]をメタクリル樹脂組成物[x2]に変えた以外は、実施例1bと同じ方法にて厚さ60μmのメタクリル樹脂組成物[x2]からなる層と厚さ940μmのポリカーボネートからなる層とからなる総厚さ1000μmの積層シートを得た。積層シートの評価結果を表2に示す。 <Example 2b>
A layer composed of a methacrylic resin composition [x2] having a thickness of 60 μm and a polycarbonate having a thickness of 940 μm were prepared in the same manner as in Example 1b except that the methacrylic resin composition [x1] was changed to a methacrylic resin composition [x2]. A laminated sheet having a total thickness of 1000 μm was obtained. The evaluation results of the laminated sheet are shown in Table 2.
メタクリル樹脂組成物[x1]をメタクリル樹脂組成物[x3]に変えた以外は、実施例1bと同じ方法にて厚さ60μmのメタクリル樹脂組成物[x3]からなる層と厚さ940μmのポリカーボネートからなる層とからなる総厚さ1000μmの積層シートを得た。積層シートの評価結果を表2に示す。 <Example 3b>
A layer composed of a methacrylic resin composition [x3] having a thickness of 60 μm and a polycarbonate having a thickness of 940 μm were prepared in the same manner as in Example 1b except that the methacrylic resin composition [x1] was changed to a methacrylic resin composition [x3]. A laminated sheet having a total thickness of 1000 μm was obtained. The evaluation results of the laminated sheet are shown in Table 2.
メタクリル樹脂組成物[x1]をメタクリル樹脂組成物[x4]に変えた以外は、実施例1bと同じ方法にて厚さ60μmのメタクリル樹脂組成物[x4]からなる層と厚さ940μmのポリカーボネートからなる層とからなる総厚さ1000μmの積層シートを得た。積層シートの評価結果を表2に示す。 <Example 4b>
Except for changing the methacrylic resin composition [x1] to the methacrylic resin composition [x4], a layer composed of the methacrylic resin composition [x4] having a thickness of 60 μm and a polycarbonate having a thickness of 940 μm were prepared in the same manner as in Example 1b. A laminated sheet having a total thickness of 1000 μm was obtained. The evaluation results of the laminated sheet are shown in Table 2.
メタクリル樹脂組成物[x1]をメタクリル樹脂組成物[x5]に変えた以外は、実施例1bと同じ方法にて厚さ60μmのメタクリル樹脂組成物[x5]からなる層と厚さ940μmのポリカーボネートからなる層とからなる総厚さ1000μmの積層シートを得た。積層シートの評価結果を表2に示す。 <Comparative Example 1b>
A layer composed of a methacrylic resin composition [x5] having a thickness of 60 μm and a polycarbonate having a thickness of 940 μm were prepared in the same manner as in Example 1b except that the methacrylic resin composition [x1] was changed to a methacrylic resin composition [x5]. A laminated sheet having a total thickness of 1000 μm was obtained. The evaluation results of the laminated sheet are shown in Table 2.
メタクリル樹脂組成物[x1]をメタクリル樹脂組成物[x6]に変えた以外は、実施例1bと同じ方法にて厚さ60μmのメタクリル樹脂組成物[x6]からなる層と厚さ940μmのポリカーボネートからなる層とからなる総厚さ1000μmの積層シートを得た。積層シートの評価結果を表2に示す。 <Comparative Example 2b>
A layer composed of a methacrylic resin composition [x6] having a thickness of 60 μm and a polycarbonate having a thickness of 940 μm were prepared in the same manner as in Example 1b except that the methacrylic resin composition [x1] was changed to a methacrylic resin composition [x6]. A laminated sheet having a total thickness of 1000 μm was obtained. The evaluation results of the laminated sheet are shown in Table 2.
メタクリル樹脂組成物[x1]をメタクリル樹脂組成物[x7]に変えた以外は、実施例1bと同じ方法にて厚さ60μmのメタクリル樹脂組成物[x7]からなる層と厚さ940μmのポリカーボネートからなる層とからなる総厚さ1000μmの積層シートを得た。積層シートの評価結果を表2に示す。 <Comparative Example 3b>
A layer composed of a methacrylic resin composition [x7] having a thickness of 60 μm and a polycarbonate having a thickness of 940 μm were prepared in the same manner as in Example 1b except that the methacrylic resin composition [x1] was changed to a methacrylic resin composition [x7]. A laminated sheet having a total thickness of 1000 μm was obtained. The evaluation results of the laminated sheet are shown in Table 2.
メタクリル樹脂組成物[x1]をメタクリル樹脂[A]に変えた以外は、実施例1bと同じ方法にて厚さ60μmのメタクリル樹脂[A]からなる層と厚さ940μmのポリカーボネートからなる層とからなる総厚さ1000μmの積層シートを得た。積層シートの評価結果を表2に示す。 <Comparative Example 4b>
Except for changing the methacrylic resin composition [x1] to the methacrylic resin [A], the same method as in Example 1b was used. From the layer made of methacrylic resin [A] having a thickness of 60 μm and the layer made of polycarbonate having a thickness of 940 μm A laminated sheet having a total thickness of 1000 μm was obtained. The evaluation results of the laminated sheet are shown in Table 2.
Claims (12)
- メタクリル酸脂環式炭化水素エステルに由来する構造単位とその他の単量体に由来する構造単位とからなる共重合体(a)100質量部と、
高級アルコール、炭化水素、脂肪酸、脂肪酸金属塩、脂肪族アミド、および1分子中に水酸基を2以上有しない脂肪酸エステルからなる群より選ばれる少なくとも一つからなる滑剤(x)0.001質量部以上2質量部以下と、
炭素原子数10~24の飽和脂肪酸のモノグリセライドからなる滑剤(y1)0~0.1質量部と
を含有する樹脂組成物。 100 parts by mass of a copolymer (a) composed of a structural unit derived from a methacrylic acid alicyclic hydrocarbon ester and a structural unit derived from another monomer;
Lubricant (x) consisting of at least one selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters having no two or more hydroxyl groups in one molecule (x) 0.001 parts by mass or more 2 parts by mass or less,
A resin composition comprising 0 to 0.1 parts by mass of a lubricant (y1) comprising a monoglyceride of a saturated fatty acid having 10 to 24 carbon atoms. - 滑剤(y1)の含有量が、共重合体(a)100質量部に対して0~0.05質量部である請求項1に記載の樹脂組成物。 The resin composition according to claim 1, wherein the content of the lubricant (y1) is 0 to 0.05 parts by mass with respect to 100 parts by mass of the copolymer (a).
- 滑剤(y1)の含有量が、共重合体(a)100質量部に対して0~0.01質量部である請求項1に記載の樹脂組成物。 The resin composition according to claim 1, wherein the content of the lubricant (y1) is 0 to 0.01 parts by mass with respect to 100 parts by mass of the copolymer (a).
- メタクリル酸脂環式炭化水素エステルに由来する構造単位とその他の単量体に由来する構造単位とからなる共重合体(a)100質量部と、
高級アルコール、炭化水素、脂肪酸、脂肪酸金属塩、脂肪族アミド、および1分子中に水酸基を2以上有しない脂肪酸エステルからなる群より選ばれる少なくとも一つからなる滑剤(x)0.001質量部以上2質量部以下と、
1分子中に水酸基を2以上有する脂肪酸エステルからなる滑剤(y2)0~0.1質量部と
を含有する樹脂組成物。 100 parts by mass of a copolymer (a) composed of a structural unit derived from a methacrylic acid alicyclic hydrocarbon ester and a structural unit derived from another monomer;
Lubricant (x) consisting of at least one selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters having no two or more hydroxyl groups in one molecule (x) 0.001 parts by mass or more 2 parts by mass or less,
A resin composition comprising 0 to 0.1 parts by mass of a lubricant (y2) comprising a fatty acid ester having two or more hydroxyl groups in one molecule. - 滑剤(y2)の含有量が、共重合体(a)100質量部に対して0~0.05質量部である請求項4に記載の樹脂組成物。 The resin composition according to claim 4, wherein the content of the lubricant (y2) is 0 to 0.05 parts by mass with respect to 100 parts by mass of the copolymer (a).
- 滑剤(y2)の含有量が、共重合体(a)100質量部に対して0~0.01質量部である請求項4に記載の樹脂組成物。 The resin composition according to claim 4, wherein the content of the lubricant (y2) is 0 to 0.01 parts by mass with respect to 100 parts by mass of the copolymer (a).
- 滑剤(x)が、炭素原子数12~18の脂肪族1価アルコールおよび炭素原子数16~24の飽和脂肪酸からなる群より選ばれる少なくとも一つからなるものである請求項1~6のいずれかひとつに記載の樹脂組成物。 7. The lubricant (x) is composed of at least one selected from the group consisting of aliphatic monohydric alcohols having 12 to 18 carbon atoms and saturated fatty acids having 16 to 24 carbon atoms. The resin composition as described in one.
- ガラス転移温度が115℃以上150℃以下である請求項1~7のいずれかひとつに記載の樹脂組成物。 The resin composition according to any one of claims 1 to 7, which has a glass transition temperature of 115 ° C or higher and 150 ° C or lower.
- 23℃の水中における飽和吸水率が0.3~1.8質量%である請求項1~8のいずれかひとつに記載の樹脂組成物。 The resin composition according to any one of claims 1 to 8, wherein the saturated water absorption in water at 23 ° C is 0.3 to 1.8% by mass.
- 請求項1~9のいずれかひとつに記載の樹脂組成物からなる成形品。 A molded article comprising the resin composition according to any one of claims 1 to 9.
- 請求項1~9のいずれかひとつに記載の樹脂組成物からなる層と、
ガラス転移温度が130℃以上160℃以下である熱可塑性樹脂組成物からなる層とを有する積層体。 A layer comprising the resin composition according to any one of claims 1 to 9,
And a layer made of a thermoplastic resin composition having a glass transition temperature of 130 ° C. or higher and 160 ° C. or lower. - ガラス転移温度が130℃以上160℃以下である熱可塑性樹脂組成物がポリカーボネートを含有する樹脂組成物である請求項11に記載の積層体。 The laminate according to claim 11, wherein the thermoplastic resin composition having a glass transition temperature of 130 ° C or higher and 160 ° C or lower is a resin composition containing polycarbonate.
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WO2018221580A1 (en) * | 2017-05-31 | 2018-12-06 | 株式会社クラレ | Layered film, layered molded body, and methods for producing these |
CN111670105A (en) * | 2018-02-02 | 2020-09-15 | 三菱化学株式会社 | Material for three-dimensional molding, filament for three-dimensional molding, wound body of the filament, and three-dimensional printer cartridge |
WO2023120305A1 (en) * | 2021-12-20 | 2023-06-29 | 三菱ケミカル株式会社 | Methacrylic resin composition for injection molding or extrusion molding, resin molded body and method for producing same |
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CN105555863B (en) | 2017-07-18 |
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