JPWO2015041311A1 - Resin composition and molded product thereof - Google Patents

Abstract

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, a higher alcohol, a hydrocarbon, a fatty acid, an aliphatic amide, And a lubricant (x) consisting of at least one selected from the group consisting of fatty acid esters having no two or more hydroxyl groups in one molecule and 0.001 to 2 parts by mass of a fatty acid having two or more hydroxyl groups in one molecule The resin composition containing the lubricant (y2) which consists of ester 0.1 mass part or less. The resin composition is melt-molded to obtain a molded product.

Description

  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.

  The 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). 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

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.

  In order to solve the above problems, the present invention including the following embodiments has been completed.

[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.

[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).

[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 containing 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.

[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).

[7] The lubricant (x) is composed of at least one selected from the group consisting of an aliphatic monohydric alcohol having 12 to 18 carbon atoms and a saturated fatty acid 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.

[10] A molded article 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.

  The resin composition according to the present invention has excellent heat resistance, and no gel is produced 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 comprises 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).

（式（I）中、Ｃｙは脂環式炭化水素基を表す。）

(In formula (I), Cy represents an alicyclic hydrocarbon group.)

Examples of methacrylic acid alicyclic hydrocarbon esters include methacrylic acid monocyclic aliphatics such as cyclohexyl methacrylate, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, cyclopentyl methacrylate, cycloheptyl methacrylate, menthyl methacrylate, and the like. Hydrocarbon ester; 2-norbornyl methacrylate, 2-methyl-2-norbornyl methacrylate, 2-ethyl-2-norbornyl methacrylate, 2-isobornyl methacrylate, 2-methyl-2-isobornyl methacrylate 2-ethyl-2-isobornyl methacrylate, 8-tricyclo [5.2.1.0 ^2,6 ] decanyl methacrylate, 8-methyl-8-tricyclo [5.2.1.0 ^2,6 ] Decanyl methacrylate, 8-ethyl-8-tricy Black [5.2.1.0 ^2,6 ] decanyl methacrylate, 2-adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, 1-adamantyl methacrylate, 2-fentyl methacrylate Methacrylic acid polycyclic aliphatic hydrocarbon esters such as 2-methyl-2-phentyl methacrylate and 2-ethyl-2-phentyl methacrylate; Among these, methacrylic acid polycyclic aliphatic hydrocarbon ester is preferable, and 8-tricyclo [5.2.1.0 ^2,6 ] decanyl methacrylate (also known as dicyclopentanyl methacrylate) is more preferable.

  In the copolymer (a) used in the present invention, 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 30-40 mass%. When the amount is less than the above range, the heat resistance of the resin composition may be inferior. When it is more than the above range, the impact resistance of the resin composition may be inferior.

  The other monomer which comprises the copolymer (a) used for this invention will not be specifically limited if it can be copolymerized with 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-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate, and phenyl acrylate; methyl methacrylate, ethyl methacrylate, n-propylene methacrylate , Isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, Methacrylic acid alkyl esters such as pentadecyl methacrylate, dodecyl methacrylate, phenyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid; ethylene, propylene, 1-butene, isobutylene, Olefins such as 1-octene; conjugated dienes such as butadiene, isoprene and myrcene; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene and m-methylstyrene; acrylamide, methacryl Examples thereof include amide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride. Among these other monomers, those obtained by combining methyl methacrylate and acrylic acid ester are preferred, and those obtained by combining methyl methacrylate and methyl acrylate are preferred.

In the copolymer (a) suitably used in the present invention, the content of the structural unit derived from methyl methacrylate is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and still more preferably 60 to 60%. 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 glass transition temperature of the copolymer (a) used in 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. When the glass transition temperature of the copolymer (a) is within the above range, the resin composition has a good balance of heat resistance and impact resistance. For example, 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. When 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.

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.

  In obtaining the copolymer (a) used in the present invention, the yellow index of the monomer mixture subjected to polymerization is preferably 2 or less, 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 according to JIS K7373 based on a value measured according to JIS Z8722 using a colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. .

  The dissolved oxygen content of 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. 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 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.

  The polymerization initiator used for production of the copolymer (a) is not particularly limited as long as it generates a reactive radical. For example, t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxypivalate 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-methylbutyronitrile), dimethyl 2,2′-azobis (2-methyl Tilpropionate). Of these, 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. For example, 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. For example, 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- (β-thiopropionate), pentaerythritol tetrakisthiopropionate; α-methylstyrene Dimer; terpinolene and the like can be mentioned. Of these, alkyl mercaptans such as n-octyl mercaptan and pentaerythritol tetrakisthiopropionate are preferred. These chain transfer agents can be used alone or in combination of two or more. The amount of the 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.
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.

  Examples of the higher alcohol 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.

  Examples of the fatty acid 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 stains and roll stains. The saturated fatty acid of several 16-24 is more preferable.

As fatty acid metal salts, 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, lead dibasic 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. A saturated fatty acid having 16 to 24 carbon atoms is more preferable. 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.

  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. Preferably, 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. Specifically, 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. It is 10 or more, more preferably 16-24.

  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 one embodiment of the present invention is composed of a monoglyceride of a saturated fatty acid having 10 to 24 carbon atoms. Examples of 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. Examples of the fatty acid ester having two or more hydroxyl groups in one molecule include polyhydric alcohol fatty acid partial esters. Specifically, 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. In the fatty acid ester having two or more hydroxyl groups in one molecule, the number of carbon atoms of the fatty acid is preferably 10 to 40, more preferably 10 to 24, and still more preferably 14 to 24. 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. When 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. Such 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. For example, in 100 parts by mass of the resin composition of the present invention, 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.

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 resin 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 Polyamides 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. .

  The method for preparing the resin composition according to the present invention is not particularly limited. For example, 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. When the glass transition temperature of the resin composition is within the above range, the resin composition has a good balance of heat resistance and impact resistance. For example, 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.

  In addition, 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. When the saturated water absorption is within the above range, warpage of the laminate due to moisture absorption can be suppressed. 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. 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 laminated body which concerns on one Embodiment of this invention has at least 1 layer which consists of resin composition [a], and at least 1 layer which consists of resin composition [b].

  The resin contained in the resin composition [b] is not particularly limited. Examples of the resin include polyolefins such as polyethylene and polypropylene, polystyrene, (meth) acrylic resin, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, and polyfluoride. Vinylidene chloride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin, polyether ether ketone, polysulfone, polyphenylene oxide, polyimide, polyether imide; thermosetting resins such as phenol resin, melamine resin, silicone resin, epoxy resin; An energy ray curable resin can be used. These resins can be used alone or in combination of two or more. Of these, thermoplastic resins are preferable, and polycarbonate is more preferable.

  When polycarbonate is employed as the resin, 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 a 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. In addition, 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 ΔTg 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. For example, 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. Of the functional layer [c], for example, 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. As for functional layer [c], only 1 type may be provided and multiple types may be provided.

  The layer structure in the laminated body of the present invention is not particularly limited. As the stacking order of the laminate of the present invention, the layer made of the resin composition [a] is the [a] layer, the layer made of the resin composition [b] is the [b] layer, and 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, [c] layer / [a] layer / [b] layer / [a] layer / [c] layer, and a) layer / [b] layer / [c] layer / [b] layer / [a] layer. For example, 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 in a laminated sheet having a shape such as a sheet, a thin plate, and a film. When 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). For example, 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, and more preferably in the range of 0.03 mm to 0.3 mm. More preferably, the thickness is in the range of 0.05 to 0.1 mm. When 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.

  From the viewpoint of suppressing the occurrence of warpage under high temperature and high humidity, it is preferable that 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. . 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 employed 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. 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.

  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 protection mask, vending machine display Electronic equipment parts such as lay covers; Medical equipment parts such as incubators and X-ray parts; Equipment-related parts such as machine covers, instrument covers, experimental equipment, rulers, dials, observation windows; LCD protective plates, light guide plates, light guides Optical components such as films, Fresnel lenses, lenticular lenses, front plates and diffusers for various displays; traffic-related components such as road signs, guide plates, curved mirrors, and noise barriers; surface materials for automobile interiors, surface materials for mobile phones Film members such as marking films; canopy materials for washing machines, control panels, top panels for rice cookers, etc .; greenhouses, large aquariums, box aquariums, clock panels, bathtubs, sanitary, desk mats, A game part, a toy, a mask for face protection at the time of welding, etc. can be mentioned.

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.

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.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

  The physical properties of the methacrylic resins and methacrylic resin compositions obtained in Production Examples, Examples 1a to 4a and Comparative Examples 1a to 3a were measured by the following methods.

<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.

<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 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 mass−initial mass) / initial mass] × 100

<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.

  While stirring the inside of the autoclave, 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.

<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.

<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].

<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].

<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].

<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].

  As the above result shows, the resin composition (Examples 1a to 4a) according to the present invention has a high glass transition temperature and a low water absorption.

  The laminated sheets obtained in Examples 1b to 4b and Comparative Examples 1b to 4b were evaluated by the following methods.

<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 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 ×.

<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.

<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.

<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.

<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.

<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.

<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.

<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.

<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.

  As the above results show, the laminates (Examples 1b to 4b) according to the present invention have few foreign matter defects due to gels or 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.

Claims (12)

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.   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).   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). 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 containing 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 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).   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).   The lubricant (x) is composed of at least one selected from the group consisting of an aliphatic monohydric alcohol having 12 to 18 carbon atoms and a saturated fatty acid having 16 to 24 carbon atoms. The resin composition as described in one.   The resin composition according to claim 1, which has a glass transition temperature of 115 ° C. or higher and 150 ° C. or lower.   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.   A molded article comprising the resin composition according to any one of claims 1 to 9. 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.   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.