KR102451853B1 - Resin composition, molded article and laminate - Google Patents

Abstract

A resin composition containing a methacrylic resin and a lubricant, in which a gel is not easily formed during melt molding, and the like are provided. The resin composition of the present invention is a resin mixture (M) containing a methacrylic resin (A), a vinyl copolymer (B) containing a structural unit of the formula (1) and a structural unit of the formula (2), and a lubricant; contains With respect to 100 parts by mass of the resin mixture (M), the lubricant satisfies the conditions of (i) and (ii). (i) Lubricating agent (x1) which consists of monoglyceride of C10-C24 saturated fatty acid is not contained, or it is 0.1 mass part or less. (ii) higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides and fatty acid esters (provided that the lubricant (x1) and a lubricant (x2) comprising a fatty acid ester having two or more hydroxyl groups in one molecule other than the lubricant (x1) excluded) is 0.001 to 2 parts by mass of the lubricant (Y) consisting of at least one selected from the group consisting of (R ¹ and R ² in Formula (1) each independently represent a hydrogen atom or an alkyl group) (R ³ and R ⁴ in Formula (2) each independently represent a hydrogen atom or an alkyl group)

Description

A resin composition, a molded article, and a laminated body {RESIN COMPOSITION, MOLDED ARTICLE AND LAMINATE}

The present invention relates to a resin composition containing a methacrylic resin, a vinyl-based copolymer, and a lubricant. Moreover, it is related with the molded article and laminated body containing the said resin composition.

A lubricating agent may be contained in the methacrylic resin excellent in transparency, abrasion resistance, weather resistance, etc. for the purpose of improving releasability, workability, etc. (for example, patent documents 1, 2). However, by containing the lubricant, the physical properties are improved while the heat resistance and moisture resistance are lowered. Since the fall of heat resistance causes a dimensional change of the molded object using such a methacrylic resin composition, it becomes a problem in the use which dimensional accuracy is calculated|required. Moreover, the fall of moisture resistance also poses a problem for the same reason.

As a resin with high heat resistance and moisture resistance, the copolymer resin which consists of styrene and maleic anhydride is known. For example, in Nonpatent Document 1, it is reported that the copolymer resin which consists of styrene and maleic anhydride containing 18-35 mass % of maleic anhydride is high heat resistance compared with a methacryl resin. Moreover, in Nonpatent Document 2, there is a description to the effect that a copolymer resin of styrene and maleic anhydride becomes a low water-absorbent resin, and in Patent Documents 3 and 4, a copolymer resin composed of styrene and maleic anhydride is used as a methacrylic resin. A composition blended in is disclosed.

Japanese Patent Laid-Open No. 2012-180454 Japanese Patent No. 3400104 International Publication No. 2014/021264 Japanese Patent Application Laid-Open No. 2014-160583

XIRAN(R)SMA "New tricks in polymer blends" [POLYSCOPE company] (http://www.bpri.org/documenten/2008_8_flippo.pdf) THOMASNET NEWS "Polyscope Polymers Expands Scope of XIRAN(R)SMA as Additive for Amorphous Thermoplastics" [2010, POLYSCOPE] (http://news.thomasnet.com/companystory/Polyscope-Polymers-Expands-Scope-of-XIRAN) -SMA-as-Additive-for-Amorphous-Thermoplastics-573050)

However, when a resin composition with improved heat resistance and moisture resistance contains a lubricant and melt molding is performed under high temperature conditions, high molecular weight droplet foreign substances, ie, gels, may be produced by crosslinking. . There is a problem that the gel becomes a defect of foreign substances in the molded article or impairs the appearance of the product.

Moreover, although filtration with a filter is performed at the time of melt-molding in the specific use which a high-quality external appearance is requested|required, there also existed a problem that gelatinization was encouraged by this filtration. That is, filter filtration has the effect of capturing and pulverizing gels in the resin composition generated in the polymerization process, including contamination, or gels generated up to the front of the filter in the melt molding process, while the resin stays in the filter for a long time to prevent gelation. There was a problem with steering.

The present invention has been made in view of the above problems, and its object is to provide a resin composition, a molded article, and a laminate in which a resin composition containing a methacrylic resin and a lubricant does not easily generate a gel during melt molding. will do

As a result of repeating earnest research by this inventor etc., in the following aspects, it discovered that the said subject could be solved, and came to complete this invention.

[1] 5-90 mass % of the methacrylic resin (A), a structural unit derived from the aromatic vinyl compound (b1) represented by the following general formula (1), and a cyclic acid anhydride (b2) represented by the following general formula (2) ) containing a resin mixture (M) containing 10 to 95 mass% of a vinyl copolymer (B) at least composed of structural units derived from ), and a lubricant, A resin composition satisfying the conditions.

(i) The lubricant (x1) composed of monoglyceride of saturated fatty acid having 10 to 24 carbon atoms is not contained or is 0.1 parts by mass or less with respect to 100 parts by mass of the resin mixture (M).

(ii) higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters (provided that the lubricant (x1) and a lubricant comprising a fatty acid ester having two or more hydroxyl groups in one molecule other than the lubricant (x1) (x2) 0.001 to 2 parts by mass of at least one lubricant (Y) selected from the group consisting of) is contained in an amount of 0.001 to 2 parts by mass based on 100 parts by mass of the resin mixture (M).

[Formula 1]

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group)

[Formula 2]

(R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group)

[2] The resin composition according to [1], wherein the lubricant (Y) is 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.

[3] The resin composition according to [1] or [2], wherein the resin mixture (M) contains 30 to 60 mass% of the methacrylic resin (A) and 40 to 70 mass% of the vinyl copolymer (B).

[4] The vinyl copolymer (B) contains 50 to 84 mass% of the structural unit derived from the aromatic vinyl compound (b1), and 15 to 49 mass% of the structural unit derived from the cyclic acid anhydride (b2) The resin composition according to any one of [1] to [3], which contains 1 to 35 mass% of a structural unit derived from methacrylic acid ester (b3).

[5] The resin composition according to [4], wherein the methacrylic acid ester (b3) is methyl methacrylate.

[6] The resin composition according to any one of [1] to [5], wherein the glass transition temperature is 115 to 160°C.

[7] The resin composition according to any one of [1] to [6], wherein the saturated water absorption in water at 23°C is 0.3 to 1.9 mass%.

[8] The resin composition according to any one of [1] to [7], wherein the lubricant further satisfies the following conditions (iii) and (iv).

(iii) The lubricant (x2) is not contained or is 0.1 parts by mass or less with respect to 100 parts by mass of the resin mixture (M).

(iv) The total amount of the lubricant (x1) and the lubricant (x2) is in the range of 0 to 0.1 with respect to 100 parts by mass of the resin mixture (M).

[9] The resin composition according to any one of [1] to [8], wherein the total amount of the lubricant is 0.1 parts by mass or more with respect to 100 parts by mass of the resin mixture (M).

[10] A molded article comprising the resin composition according to any one of [1] to [9].

[11] A laminate comprising a layer comprising the resin composition (C1) according to any one of [1] to [9] and a layer comprising the thermoplastic resin composition (T) having a glass transition temperature in the range of 130 to 160°C sifter.

[12] The laminate according to [11], wherein the thermoplastic resin composition (T) is a resin composition containing polycarbonate.

[13] The laminate according to [11] or [12], wherein the difference between the glass transition temperature of the thermoplastic resin composition (T) and the resin composition is 30°C or less.

[14] The laminate according to any one of [11] to [13], further comprising a scratch-resistant layer on at least one surface.

The resin composition according to the present invention is a resin composition containing a methacrylic resin, an aromatic vinyl-cyclic acid anhydride copolymer and a lubricant, and provides a resin composition, a molded article, and a laminate in which a gel is not easily generated during melt molding. It has a great effect that it can do.

Hereinafter, an example of embodiment to which this invention is applied is demonstrated. In addition, the numerical value specified in this specification shows the value obtained when measuring by the method described in the Example mentioned later. For example, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are standard polystyrene conversion values measured by GPC (gel permeation chromatography), and are obtained when measured by the method described in Examples to be described later. value is indicated. In addition, the numerical values "A-B" specified in this specification are a value larger than numerical value A and numerical value A, and show the range which satisfy|fills the value smaller than numerical value B and numerical value B.

[resin composition]

The resin composition of the present invention comprises a methacrylic resin (A), a structural unit derived from an aromatic vinyl compound (b1) represented by the following general formula (1), and a cyclic acid anhydride (b2) represented by the following general formula (2) 100 parts by mass of a resin mixture (M) containing a vinyl copolymer (B) (hereinafter referred to as "SMA resin (B)") containing a structural unit derived from , and a specific lubricant.

[Formula 3]

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group)

[Formula 4]

(R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group)

[Resin mixture (M)]

The resin mixture (M) which concerns on this invention contains a methacrylic resin (A) and an SMA resin (B).

Content of the methacrylic resin (A) in a resin mixture (M) is the range of 5-90 mass %. It is preferable that content of the methacrylic resin (A) in resin mixture (M) is 10 mass % or more, It is more preferable that it is 15 mass % or more, It is more preferable that it is 20 mass % or more, It is most preferable that it is 30 mass % or more. . Further, the content of the methacrylic resin (A) in the resin mixture (M) is preferably 85 mass% or less, more preferably 80 mass% or less, still more preferably 75 mass% or less, and most preferably 60 mass% or less. desirable. When the layer made of the resin composition of the present invention has excellent scratch resistance when the content of the methacrylic resin (A) in the resin mixture (M) is 5 mass% or more, and is 90 mass% or less, when laminated with another layer Generation|occurrence|production of the curvature in high temperature, high humidity can be suppressed.

A methacrylic resin (A) is resin containing the structural unit derived from methacrylic acid ester. Examples of such methacrylic acid esters include methyl methacrylate (hereinafter referred to as "MMA"), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methacrylic acid. Sobutyl, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, methacrylate such as dodecyl methacrylate acrylic acid alkyl ester; Methacrylic acid such as 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, and tricyclo[5.2.1.0 ^2,6 ]deca-8-yl methacrylate cycloalkyl ester; methacrylic acid aryl esters such as phenyl methacrylate; methacrylic acid aralkyl esters such as benzyl methacrylate; and the like, and from the viewpoint of availability, MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert- methacrylate Butyl is preferred, and MMA is most preferred. 90 mass % or more is preferable, as for content of the structural unit derived from the methacrylic acid ester in a methacrylic resin (A), 95 mass % or more is more preferable, 98 mass % or more is still more preferable, methacrylic acid Only the structural unit derived from ester may be sufficient.

Moreover, from a heat resistant viewpoint, it is preferable that the methacrylic resin (A) contains 90 mass % or more of structural units derived from MMA, It is more preferable to contain 95 mass % or more, It is to contain 98 mass % or more More preferably, only the structural unit derived from MMA may be sufficient.

Moreover, the methacrylic resin (A) may contain the structural unit derived from other monomers other than methacrylic acid ester. Examples of such other monomers include methyl acrylate (hereinafter referred to as "MA"), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-acrylic acid Ethylhexyl, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, acrylic acid 3-methoxybutyl, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 3-acrylic acid and acrylic acid esters such as dimethylaminoethyl, and from the viewpoint of availability, acrylic acid esters such as MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate are preferable. and MA and ethyl acrylate are more preferable, and MA is the most preferable. 10 mass % or less is preferable in total, as for content of the structural unit derived from these other monomers in a methacryl resin (A), 5 mass % or less is more preferable, and its 2 mass % or less is still more preferable.

A methacrylic resin (A) is obtained by superposing|polymerizing said methacrylic acid ester independent or methacrylic acid ester, and the other monomer which is an arbitrary component. In such polymerization, when a plurality of types of monomers are used, the monomer mixture is usually prepared by mixing the plurality of types of monomers, and then subjected to polymerization. Although there is no restriction|limiting in particular in the polymerization method, From a viewpoint of productivity, it is preferable to carry out radical polymerization by methods, such as a block polymerization method, suspension polymerization method, solution polymerization method, and emulsion polymerization method.

As for the weight average molecular weight (henceforth "Mw") of a methacryl resin (A), 40,000-500,000 are preferable. When this Mw is 40,000 or more, the laminate of the present invention has excellent scratch resistance and heat resistance, and when it is 500,000 or less, the resin mixture (M) has excellent moldability, and the productivity of the laminate of the present invention can be increased. .

Content of SMA resin (B) in resin mixture (M) is the range of 10-95 mass %. The content of the SMA resin (B) in the resin mixture (M) is preferably 15 mass% or more, more preferably 20 mass% or more, still more preferably 25 mass% or more, and most preferably 40 mass% or more. The content of the SMA resin (B) in the resin mixture (M) is preferably 90 mass% or less, more preferably 85 mass% or less, still more preferably 80 mass% or less, and most preferably 70 mass% or less. . When the layer made of the resin composition of the present invention has a content of the SMA resin (B) in the resin mixture (M) of 10% by mass or more, it is possible to suppress the occurrence of warpage under high temperature and high humidity when laminated with other layers, It is excellent in abrasion resistance because it is 95 mass % or less.

The SMA resin (B) is a vinyl copolymer (B) comprising at least a structural unit (b1) derived from an aromatic vinyl compound and a structural unit (b2) derived from a cyclic acid anhydride.

Examples of the alkyl group each independently represented by R ¹ and R ² in the general formula (1) and R ³ and R ⁴ in the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group An alkyl group having 12 or less carbon atoms, such as , decyl group and dodecyl group, is preferable, and a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, etc. An alkyl group having 4 or less carbon atoms is more preferable.

As R ¹ , a hydrogen atom, a methyl group, an ethyl group and a t-butyl group are preferable. As R ² , R ³ , and R ⁴ , a hydrogen atom, a methyl group, and an ethyl group are preferable.

The content of the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is preferably 50 mass% or more, more preferably 55 mass% or more, and still more preferably 60 mass% or more. Further, the content of the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is preferably 84 mass% or less, more preferably 82 mass% or less, and still more preferably 80 mass% or less. If this content is in the range of 50-84 mass %, the resin mixture (M) will be excellent in moisture resistance and transparency. However, when the SMA resin (B) consists of two monomers, an aromatic vinyl compound (b1) and a cyclic acid anhydride (b2), the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is It is preferable to make content into the range of 50-85 mass %.

As an aromatic vinyl compound (b1), For example, styrene; each alkyl-substituted styrene such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, and 4-tert-butylstyrene; α-alkyl-substituted styrenes such as α-methylstyrene and 4-methyl-α-methylstyrene; , and styrene is preferable from the viewpoint of availability. These aromatic vinyl compounds (b1) may be used individually by 1 type, and may use multiple types together.

The content of the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) is preferably 15 mass% or more, more preferably 18 mass% or more, and still more preferably 20 mass% or more. Further, the content of the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) is preferably 49 mass% or less, more preferably 45 mass% or less, and still more preferably 40 mass% or less. When this content exists in the range of 15-49 mass %, the resin mixture (M) becomes a thing excellent in heat resistance and transparency. However, when the SMA resin (B) consists of two monomers, an aromatic vinyl compound (b1) and a cyclic acid anhydride (b2), a structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B). It is preferable to make content into the range of 15-50 mass %.

As cyclic acid anhydride (b2), maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, etc. are mentioned, for example, From a viewpoint of availability, maleic anhydride is preferable. A cyclic acid anhydride (b2) may be used individually by 1 type, and may use multiple types together.

The SMA resin (B) preferably contains a structural unit derived from methacrylic acid ester in addition to the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2). It is preferable that content of the structural unit derived from the methacrylic acid ester (b3) in SMA resin (B) is 1 mass % or more, It is more preferable that it is 3 mass % or more, It is still more preferable that it is 5 mass % or more. Moreover, it is preferable that content of the structural unit derived from the methacrylic acid ester (b3) in SMA resin (B) is 35 mass % or less, It is more preferable that it is 30 mass % or less, It is still more preferable that it is 26 mass % or less. When this content exists in the range of 1-35 mass %, it becomes the thing excellent in transparency and thermal stability.

Examples of the methacrylic acid ester (b3) include MMA, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. , 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 1-phenylethyl methacrylate; and the like. Among these methacrylic acid esters, alkyl methacrylic acid esters having 1 to 7 carbon atoms in the alkyl group are preferred, and from the viewpoint of excellent heat resistance and transparency of the obtained SMA resin, MMA is particularly preferred. Moreover, methacrylic acid ester may be used individually by 1 type, and may use multiple types together.

The SMA resin (B) may have a structural unit derived from another monomer other than the aromatic vinyl compound (b1), the cyclic acid anhydride (b2), and the methacrylic acid ester (b3). Examples of such other monomers include MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, acrylic acid Dodecyl, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoroacrylate and acrylic acid esters such as methyl, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, and 3-dimethylaminoethyl acrylate. have. These other monomers may be used individually by 1 type, and may use multiple types together. 10 mass % or less is preferable, as for content of the structural unit derived from such another monomer in SMA resin (B), 5 mass % or less is more preferable, and its 2 mass % or less is still more preferable.

SMA resin (B) is obtained by superposing|polymerizing the monomer of at least an aromatic vinyl compound (b1) and a cyclic acid anhydride (b2). As a monomer, you may add and superpose|polymerize methacrylic acid ester (b3) and the other monomer which is an arbitrary component. In such polymerization, the monomers to be used are usually mixed to prepare a monomer mixture, and then subjected to polymerization. Although there is no restriction|limiting in particular in the polymerization method, From a viewpoint of productivity, it is preferable to carry out radical polymerization by methods, such as a block polymerization method and a solution polymerization method.

As for Mw of SMA resin (B), the range of 40,000-300,000 is preferable. When this Mw is 40,000 or more, the laminate of the present invention is excellent in scratch resistance and impact resistance, and when it is 300,000 or less, the resin mixture (M) is excellent in moldability and productivity of a molded article comprising the resin composition of the present invention can increase

The mass ratio (methacrylic resin (A)/SMA resin (B)) of the methacryl resin (A) and the SMA resin (B) contained in the resin mixture (M) suppresses the occurrence of warpage under high temperature and high humidity, transparency , it is preferably in the range of 5/95 to 90/10 from the viewpoint of scratch resistance. It is more preferable that this mass ratio is 10/90 or more, It is still more preferable that it is 15/85 or more, It is especially preferable that it is 20/80 or more. Moreover, it is more preferable that this mass ratio is 85/15 or less, It is still more preferable that it is 80/20 or less, It is especially preferable that it is 75/25 or less.

Mixing of the methacrylic resin (A) and SMA resin (B) can use a melt mixing method, a solution mixing method, etc., for example. In the melt-mixing method, for example, a melt-kneading machine such as a single-screw or multi-screw kneader, an open roll, a Banbury mixer, or a kneader is used and, if necessary, melt-kneaded in an inert gas atmosphere such as nitrogen gas, argon gas, or helium gas. carry out In the solution mixing method, methacryl resin (A) and SMA resin (B) are melt|dissolved in organic solvents, such as toluene, tetrahydrofuran, and methyl ethyl ketone, and are mixed.

The resin mixture (M) may contain other polymers other than the methacryl resin (A) and the SMA resin (B) as long as the effect of the present invention is not impaired. Examples of such other polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene, and ethylene-based ionomers; styrene-based resins such as polystyrene, styrene-maleic anhydride copolymer, high-impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; methyl methacrylate-styrene copolymer; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon 6, nylon 66, and polyamide elastomer; Polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer , a thermoplastic resin such as polyacetal; Thermosetting resins, such as a phenol resin, a melamine resin, a silicone resin, and an epoxy resin; polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin; Acrylic rubber, silicone rubber; Styrenic thermoplastic elastomers, such as SEPS, SEBS, and SIS; Olefin rubbers, such as IR, EPR, and EPDM, etc. are mentioned. Another polymer may be used individually by 1 type, and may use multiple types together.

It is preferable that content of the other polymer in resin mixture (M) is 10 mass % or less, It is more preferable that it is 5 mass % or less, It is still more preferable that it is 2 mass % or less.

The resin mixture (M) may contain various additives as needed. Such additives include, for example, antioxidants, thermal degradation inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes/pigments, light diffusing agents, gloss removers, impact resistance modifiers, phosphors and the like. Content of these additives can be set suitably in the range which does not impair the effect of this invention, For example, content of antioxidant is 0.01-1 mass part with respect to 100 mass parts of resin mixture (M), and a ultraviolet absorber. It is preferable that content of 0.01-3 mass parts, content of a light stabilizer sets 0.01-3 mass parts, content of a lubricant sets 0.01-3 mass parts, and content of a dye and a pigment sets it as 0.01-3 mass parts.

When making the resin mixture (M) contain another polymer and/or additive, you may add when superposing|polymerizing a methacryl resin (A) and/or SMA resin (B), and a methacryl resin (A) and SMA resin (B) ) may be added when mixing, or may be added after mixing the methacrylic resin (A) and the SMA resin (B).

It is preferable that the range of the glass transition temperature of a resin mixture (M) is 120-160 degreeC. As for the lower limit of such a glass transition temperature, it is more preferable that it is 130 degreeC or more, and it is still more preferable that it is 140 degreeC or more. Moreover, it is more preferable that it is 155 degrees C or less, and, as for the upper limit of such a glass transition temperature, it is still more preferable that it is 150 degrees C or less. When a glass transition temperature is the range of 120-160 degreeC, generation|occurrence|production of the curvature in high temperature, high humidity of the molded object which consists of the resin composition of this invention can be suppressed. In addition, the glass transition temperature in this specification is a temperature at the time of using a differential scanning calorimeter, measuring at a temperature increase rate of 10 degree-C/min, and calculating by the midpoint method.

It is preferable that the melt flow rate (henceforth "MFR") of the resin mixture (M) is in the range of 1-10 g/10min. As for the lower limit of such MFR, it is more preferable that it is 1.5 g/10min or more, and it is still more preferable that it is 2.0 g/10min. Moreover, as for the upper limit of such MFR, it is more preferable that it is 7.0 g/10min or less, and it is still more preferable that it is 4.0 g/10min or less. When the MFR is in the range of 1 to 10 g/10 min, the stability of hot melt molding is good. In addition, MFR of the resin mixture (M) in this specification is the value measured under the temperature of 230 degreeC and a 3.8 kg load using a melt indexer.

[lubricant]

A lubricating agent is a well-known additive added to resin in order to provide anti-friction (減摩性) and releasability. As the lubricant, a higher alcohol lubricant, a hydrocarbon lubricant, a fatty acid lubricant, a fatty acid metal salt lubricant, an aliphatic amide lubricant, an ester lubricant, and the like are known. Among these, in the present invention, a lubricant satisfying the following conditions (i) and (ii) is used.

(i) It does not contain the lubricant (x1) which consists of monoglyceride of C10-C24 saturated fatty acid, or 0.1 mass part or less with respect to 100 mass parts of resin mixture (M).

(ii) higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters (provided that the lubricant (x1) and a lubricant comprising a fatty acid ester having two or more hydroxyl groups in one molecule other than the lubricant (x1) (x2) of at least one lubricant (Y) selected from the group consisting of) is 0.001 to 2 parts by mass based on 100 parts by mass of the resin mixture (M).

It is preferable that the total amount of a lubricant exists in the range of 0.001-3 mass parts with respect to 100 mass parts of resin mixture (M) from a viewpoint of the balance of the heat resistance of a resin composition, and the external appearance quality of a molded object. By setting it as the above range, the internal activity of the resin composition is increased without significantly lowering the heat resistance of the resin composition, and adhesion to the metal surface such as a barrel, screw, roll, etc. is prevented during melt molding such as extrusion molding, and the appearance quality is improved. An excellent molded article is obtained. The total amount of the lubricant is more preferably 0.005 parts by mass or more, still more preferably 0.01 parts by mass or more, still more preferably 0.1 parts by mass or more, and most preferably 0.15 parts by mass or more. Moreover, it is more preferable that it is 2 mass parts or less, and, as for the total amount of a lubricant, it is still more preferable that it is 1 mass part or less.

The lubricant (x1) is a lubricant composed of monoglyceride of saturated fatty acids having 10 to 24 carbon atoms, and the lubricant (x2) is a lubricant composed of a fatty acid ester having two or more hydroxyl groups in one molecule other than the lubricant (x1). to be. That is, when the lubricant (X) is a lubricant composed of a fatty acid ester having two or more hydroxyl groups in one molecule, the lubricant (X) is composed of a lubricant (x1) and a lubricant (x2), and from the lubricant (X) Excluding (x1) is the lubricant (x2).

The lubricant (Y) is at least one selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters (except for lubricants (x1) and (x2)). That is, the lubricant (Y) is obtained by excluding the lubricant (X) from higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters.

Examples of the lubricant (x1) include monoglycerides such as glycerin monostearate and glycerin monobehenate. A lubricant (x1) may be used individually by 1 type, and may be used in combination of multiple types. In addition, glycerol monostearate and stearic acid monoglyceride are terms representing the same compound.

The amount of the lubricant (x1) is set to 0 to 0.1 parts by mass with respect to 100 parts by mass of the resin mixture (M). The amount of the lubricant (x1) is preferably 0.05 parts by mass or less, more preferably 0.03 parts by mass or less, and still more preferably 0.01 parts by mass or less with respect to 100 parts by mass of the resin mixture (M). If the amount of the lubricant (x1) is too large, when the resin composition is melt-molded, it reacts with the cyclic acid anhydride (b2) unit of the vinyl-based copolymer (B) to form a gel, and foreign matter defects or poor appearance in the molded article tends to cause

Examples of the lubricant (x2) include partial esters of polyhydric alcohol fatty acids other than the lubricant (x1). Specifically, pentaerythritol mono/diesters such as pentaerythritol monostearate and pentaerythritol distearate, sorbate and sorbitan mono/diesters such as bitan monostearate and sorbitan monopalmitate.

The number of carbon atoms of the fatty acid of the lubricant (x2) is preferably 10 to 40, more preferably 10 to 24, still more preferably 14 to 24. In addition, the fatty acid may be an unsaturated fatty acid or a saturated fatty acid may be sufficient as it. A lubricant (x2) may be used individually by 1 type, and may be used in combination of multiple types.

The lubricant (Y) is at least one selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters (except for lubricants (x1) and (x2)). The lubricant (Y) is 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 having 12 to 18 carbon atoms It is an aliphatic monohydric alcohol.

The amount of the lubricant (Y) is 0.001 to 2 parts by mass with respect to 100 parts by mass of the resin mixture (M). The amount of the lubricant (Y) is preferably 0.005 parts by mass or more with respect to 100 parts by mass of the resin mixture (M), more preferably 0.01 parts by mass or more, still more preferably 0.1 parts by mass or more, and even more preferably 0.12 parts by mass or more. desirable. Moreover, it is preferable that it is 1 mass part or less with respect to 100 mass parts of resin mixture (M), and, as for the quantity of the lubricant (Y), it is more preferable that it is 0.5 mass part or less. If it is less than 0.001 parts by mass, the effect of the lubricant (Y) becomes insufficient, and even if it is more than 2 parts by mass, the additional effect of the lubricant (Y) is not obtained, but also these lubricants bleed out from the molded article, and the surface of the molded article is sticky There is a risk of distance. A lubricant (Y) can be used individually by 1 type or in combination of 2 or more type. As the lubricant (Y), it is preferable to use a plurality of lubricants (Y) having a melting point difference of 5°C or more because effects such as anti-friction properties can be exhibited in a wider temperature range.

As said higher alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, etc. are mentioned. 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 gamma property and less mold contamination and roll contamination. A saturated aliphatic monohydric alcohol having 12 to 18 atoms is more preferable, and a saturated aliphatic monohydric alcohol having 16 to 18 carbon atoms is still more preferable.

As said hydrocarbon, a C12 or more aliphatic hydrocarbon is preferable from a viewpoint of gamma property and releasability being high. Moreover, aliphatic hydrocarbons, such as liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, and polyolefin wax; partial oxides of aliphatic hydrocarbons; A commercially available thing, such as a halide of an aliphatic hydrocarbon, can be used. Even in the case of these commercially available mixtures, the contained aliphatic hydrocarbon preferably has 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, lignoseric 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, from the viewpoint of high gamma property and less mold contamination and roll contamination. 16-24 saturated fatty acids are more preferable.

Examples of the fatty acid metal salt include cadmium stearate, cadmium laurate, cadmium ricinoleate, cadmium naphthenate, cadmium 2-ethylhexophosphate, barium stearate, barium laurate, barium ricinolate, barium naphthenate, 2- Barium ethylhexophosphate, calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate, zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexophosphate, lead stearate, dibasic stearate Lead acid, 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 gamma property and less mold contamination and roll contamination. The number 16-24 saturated fatty acid is more preferable. As a metal constituting the fatty acid metal salt, from the viewpoint of stability and gamma properties, calcium, magnesium, zinc, lead, tin, iron, cadmium, aluminum, barium, cobalt, nickel, manganese, strontium, titanium, vanadium, and copper It is preferable to contain at least one metal selected from the group, and it is more preferable to contain at least one metal selected from the group consisting of calcium, magnesium, zinc and lead.

Examples of the aliphatic amide include lauric acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, oleic acid amide, eicosenic acid amide, erucic acid amide, erucic acid amide, methylenebis stearic acid amide, ethylenebisstearic acid amide, and the like. 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 contamination and roll contamination, An unsaturated fatty acid amide having 16 to 22 carbon atoms is more preferable.

The fatty acid esters (except for lubricants (x1) + lubricants (x2)) are fatty acid esters that do not have two or more hydroxyl groups in one molecule, for example, fatty acid esters of monohydric alcohols, fatty acids of dihydric alcohols. Ester etc. are mentioned, Specifically, a diglyceride, a triglyceride, an acetylated monoglyceride, stearyl stearate, a butyl stearate, ethylene glycol monostearate, ethylene glycol distearate, etc. are mentioned. The fatty acid ester used in the present invention (except lubricant (x1) + lubricant (x2)) has a high anti-friction property, and from the viewpoint of less mold staining and roll staining, the number of carbon atoms of the fatty acid in the fatty acid ester is preferable. Preferably it is 10 or more, More preferably, it is 16-24.

The lubricant of the present invention may further satisfy the following conditions (iii) and (iv). By satisfying (iii) and (iv), when the resin composition is melt-molded, foreign matter defects or poor appearance are not caused in the molded article.

(iii) The lubricant (x2) is not contained or is 0.1 parts by mass or less with respect to 100 parts by mass of the resin mixture (M).

(iv) The total of the lubricant (x1) and the lubricant (x2) is in the range of 0 to 0.1 with respect to 100 parts by mass of the resin mixture (M).

In the range that satisfies the condition (iv), the amount of the lubricant (x2) is more preferably 0.05 parts by mass or less, more preferably 0.03 parts by mass or less, and 0.01 parts by mass based on 100 parts by mass of the resin mixture (M). It is especially preferable that it is the following. When the amount of the lubricant (x2) is too large, a gel is generated when the resin composition is melt-molded, and there is a tendency to cause defects of foreign substances or poor appearance in the molded article.

In addition, the resin composition of this invention may contain various additives as needed. Such additives include, but are not limited to, heat stabilizers, antioxidants, thermal degradation inhibitors, ultraviolet absorbers, light stabilizers, inorganic fillers, inorganic or organic fibers, polymer processing aids, antistatic agents, flame retardants, salt pigments, colorants, gloss removers, light diffusers , an impact resistance modifier, a phosphor, an adhesive, a tackifier, a plasticizer, a foaming agent, etc. are mentioned. Content of these additives can be set suitably in the range which does not impair the effect of this invention. 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 parts by mass, the content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by mass, and the content of the salt pigment is preferably 0.00001 to 0.01 parts by mass. do.

The preparation method of the resin composition which concerns on this invention is not specifically limited. For example, the resin mixture (M) is kneaded at a temperature equal to or higher than the softening point, and a lubricant satisfying the requirements (i) and (ii) with respect to 100 parts by mass of the resin mixture (M) of the present invention, and an additive blended as necessary. and other polymers are added and kneaded. In addition, it can be obtained by dissolving the resin mixture (M), a lubricant satisfying the requirements (i) and (ii) of the present invention, an additive to be blended as necessary, and another polymer in a solvent, and removing the solvent from the solution. have.

The resin composition which concerns on this invention has a glass transition temperature, Preferably it is 115-160 degreeC. More preferably, it is 130-155 degreeC, More preferably, it is 140-150 degreeC. By setting the glass transition temperature of the resin composition in the range of 115 to 160°C, the resin composition has a good balance between heat resistance and impact resistance, for example, warpage occurs at high temperature and high humidity in a laminate of the resin composition and a thermoplastic resin such as polycarbonate. this is suppressed

As for the resin composition which concerns on this invention, the saturated water absorption in 23 degreeC water becomes like this. Preferably it is 0.3-1.9 mass %. More preferably, it is 0.3-1.5 mass %, More preferably, it is 0.3-1.0 mass %. The curvature of the laminated body resulting from moisture absorption can be suppressed because saturated water absorption shall be in the range of 0.3-1.9 mass %. In addition, the saturated water absorption rate is the mass of the molded article dried under vacuum for 3 days or more, the molded article is immersed in distilled water at 23 ° C., the mass is measured over time, and the mass is measured as an increase rate at the time of reaching equilibrium. is the value

Extrusion molding methods, such as a co-extrusion molding method, the T-die laminate molding method, and the extrusion coating method, for the resin composition of this invention; Injection molding methods, such as an insert injection molding method, the two-color injection molding method, the core back injection molding method, the sandwich injection molding method, the injection press molding method; blow molding method; calender molding method; press molding method; Various molded articles can be obtained by heat-melting molding by methods such as the slush molding method. Since the resin composition of the present invention does not easily form a gel even when melt-molded at high temperature for a long time, it is also suitable for manufacturing a molded article requiring high temperature and long-term residence conditions. The resin composition of this invention is suitable for manufacture of thin and wide molded articles, such as a sheet|seat, a film, a board.

[Laminate]

The laminate of the present invention has at least one layer made of the resin composition of the present invention (hereinafter also referred to as resin composition [C1]) and at least one layer made of another material. The other material used for the laminated body of this invention is not specifically limited. For example, organic materials, such as resin; Inorganic materials, such as a metal single-piece|unit and a metal oxide, are mentioned.

A laminate according to an embodiment of the present invention has at least one layer composed of the resin composition [C1] and at least one layer composed of the other layer, the resin composition [C2].

The resin contained in the resin composition [C2] is not particularly limited. Examples of the resin include polyolefin such as polyethylene and polypropylene, polystyrene, (meth)acrylic resin, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, and ethylene-vinyl. alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin, polyether ether ketone, polysulfone, polyphenylene oxide, polyimide, polyetherimide; Thermosetting resins, such as a phenol resin, a melamine resin, a silicone resin, and an epoxy resin; Energy ray-curable resin etc. are mentioned. Resin of the resin composition [C2] can be used individually by 1 type or in combination of 2 or more type. Among these, a thermoplastic resin is preferable and a polycarbonate is more preferable.

When polycarbonate is employed as the resin, the amount of polycarbonate contained in the resin composition [C2] is preferably 90 mass% or more, more preferably 95 mass% or more, and still more preferably 98 mass% or more. The weight average molecular weight of such a polycarbonate becomes like this. Preferably it is 20,000-100,000. When the weight average molecular weight of the polycarbonate is within the above range, the heat resistance and impact resistance of the resin composition [C2] are improved, and the laminated sheet composed of the resin composition [C1] and the resin composition [C2] can be formed with excellent moldability and high productivity. can be manufactured. Moreover, Mw/Mn of the said polycarbonate becomes like this. Preferably it is 1.7-2.6, More preferably, it is 1.7-2.3, More preferably, it is 1.7-2.0.

A commercial item may be used for the said polycarbonate, For example, Sumika Styron Polycarbonate Co., Ltd. make "Caliba (trademark)", Mitsubishi Engineering Plastics Co., Ltd. make "Eupiron/Novarex (trademark)", Idemitsu Kogyo Co., Ltd. "Taflon (registered trademark)" by Teijin Chemical Co., Ltd. "Panlite (registered trademark)", etc. can be used preferably.

It is preferable that the resin composition [C2] used for this invention is a thermoplastic resin composition (T) whose glass transition temperature is 130-160 degreeC. It is preferable that this thermoplastic resin composition (T) is a resin composition containing a polycarbonate. Moreover, it is preferable that the glass transition temperature of resin composition [C2] is about the same as the glass transition temperature of resin composition [C1]. Specifically, the difference ΔTg between the glass transition temperature of the resin composition [C2] and the glass transition temperature of the resin composition [C1] is preferably 30°C or less, more preferably 20°C or less. When the glass transition temperature of both resins is 30 degrees C or less, the effect which suppresses generation|occurrence|production of the curvature under high temperature, high humidity of a laminated body becomes higher.

It is preferable that the resin composition [C2] used for this invention is 0.2-0.5 mass % of saturated water absorption. Moreover, it is preferable that the saturated water absorption of the resin composition [C2] is about the same as that of the saturated water absorption of resin composition [C1]. Specifically, the difference between the saturated water absorption rates of the resin composition [C2] and the resin composition [C1], that is, the Δ saturated water absorption rate, is preferably 1.5 mass% or less, more preferably 1.0 mass% or less. The effect of suppressing generation|occurrence|production of the curvature under high temperature, high humidity of a laminated body as the saturated water absorption of both resins being about the same becomes higher.

The resin composition [C2] used in the present invention may contain a known additive in order to improve thermal decomposition resistance, heat discoloration resistance, light resistance, and the like. As additives, antioxidants, thermal degradation inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, salt pigments, light diffusers, organic dyes, gloss removers, impact modifiers, phosphors, etc. can be heard

A laminate according to another embodiment of the present invention includes at least one layer [L1] composed of a resin composition [C1], at least one layer [L2] composed of a resin composition [C2], and at least one functionally imparting layer [ L3]. The functionalization layer [L3] is not particularly limited. For example, an abrasion-resistant layer, a hard-coat layer, an antistatic layer, an antifouling|stain-resistant layer, a friction reduction layer, a glare-proof layer, an antireflection layer, an adhesion layer, an impact strength imparting layer, etc. are mentioned. The functionality imparting layer [L3] can be formed by a known method. For example, a hard-coat layer can be obtained by apply|coating the resin solution for hard-coats, drying and hardening. 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. Among the functionality imparting layers [L3], for example, an abrasion resistance layer, a hard coat layer, an antistatic layer, an antifouling layer, a friction reducing layer, an antiglare layer, an antireflection layer, etc. are generally formed on the outermost side of the laminate. As for the functional provision layer [L3], only 1 type may be provided, and multiple types may be provided. It is preferable that the laminated body of this invention has an abrasion-resistant layer on at least one surface from a viewpoint of improving abrasion resistance.

The layer structure in particular in the laminated body of this invention is not restrict|limited. In the lamination order of the laminate of the present invention, the layer made of the resin composition [C1] is the [L1] layer, the layer made of the resin composition [C2] is the [L2] layer, and the functionality imparting layer [L3] is the [L3] layer. , for example, [L1] layer/[L2] layer, [L1] layer/[L2] layer/[L1] layer, [L2] layer/[L1] layer/[L2] layer, [L1] ] layer/[L2] layer/[L1] layer/[L2] layer/[L1] layer, [L1] layer/[L2] layer/[L3] layer, [L3] layer/[L1] layer/[L2] ] layer, [L3] layer/[L1] layer/[L2] layer/[L3] layer, [L3] layer/[L1] layer/[L2] layer/[L1] layer/[L3] layer, [L1] ] layer/[L2] layer/[L3] layer/[L2] layer/[L1] layer and the like. For example, when the [L3] layer is a hard coat layer, the [L3] layer/[L1] layer/[L2] layer, the [L3] layer/[L1] layer/[L2] layer/[L3] layer, [L3] layer/[L1] layer/[L2] layer/[L1] layer/[L3] layer is preferred.

INDUSTRIAL APPLICABILITY The present invention is useful in a laminate having a shape such as a sheet, a thin plate, or a film. When the laminate according to the present invention is used as a protective cover, it is preferable to arrange so that the resin composition [C1] layer is located at the outermost side when viewed from the side to be protected (surface to be protected). For example, a laminate having a layer configuration of [L1] layer/[L2] layer is arranged in the order of [L1] layer/[L2] layer/protected surface, or [L1] layer/[L2] layer It is preferable to arrange|position the laminated body which consists of a layer structure of /[L1] layer in order of [L1] layer/[L2] layer/ [L1] layer/to-be-protected surface.

Although the total thickness of the laminated body which concerns on this invention can be set according to a use, Preferably it is 0.2-2 mm, More preferably, it is 0.3-1.5 mm. When it is too thin, there exists a tendency for rigidity to become inadequate. When too thick, there exists a tendency for weight reduction of a liquid crystal display device etc. to become a hindrance.

It is preferable that the thickness of the layer which consists of resin composition [C1] in the laminated body which concerns on this invention is the range of 0.02-0.5 mm. As for the lower limit of the thickness of such a layer, it is more preferable that it is 0.03 mm or more, and it is still more preferable that it is 0.05 mm or more. Moreover, it is more preferable that it is 0.3 mm or less, and, as for the upper limit of the thickness of such a layer, it is still more preferable that it is 0.1 mm or less. If the thickness is less than 0.01 mm, scratch resistance and weather resistance may be insufficient. Moreover, when it exceeds 0.5 mm, impact resistance may be insufficient.

From a viewpoint of suppressing generation|occurrence|production of the curvature in high temperature, high humidity, it is preferable to set it as the laminated body which concerns on this invention becomes symmetrical in the thickness direction, and it is more preferable that the thickness of each layer also becomes symmetrical.

The laminate according to the present invention is not particularly limited by its manufacturing method, for example, it can be manufactured by a multilayer molding method such as multilayer extrusion molding, multilayer blow molding, multilayer press molding, multicolor injection molding, and insert injection molding. have. Among these multilayer molding methods, from the viewpoint of productivity, multilayer extrusion molding of the resin composition [C1] and the resin composition [C2] is preferable.

The method of multi-layer extrusion molding is not particularly limited, and a known multi-layer extrusion molding method used for manufacturing a multi-layer laminate of a thermoplastic resin is employed, for example, an apparatus having a flat T-die and a polishing roll having a mirror-finished surface. is molded by As the method of the T-die, a feed block method in which the resin composition [C1] and the resin composition [C2] in a heat-melted state are laminated before entering the T-die, or the resin composition [C1] and the resin composition [C2] inside the T-die A stacked multi-manifold method or the like can be employed. From the viewpoint of improving the smoothness of the interface between the layers constituting the laminate, the multi-manifold system is preferable.

It is preferable to melt-filter the resin composition [C1] and resin composition [C2] with a filter before multilayer shaping|molding. By carrying out multilayer molding using each melt-filtered resin composition, a laminated sheet with few faults originating in a foreign material, a gel, etc. is obtained. The filter used for melt filtration is not specifically limited. The filter is appropriately selected from known ones in view of operating temperature, viscosity, and required filtration precision. As a specific example of a filter, Nonwoven fabric which consists of polypropylene, cotton, polyester, viscose rayon, glass fiber, etc.; phenol resin impregnated cellulose film; metal fiber nonwoven sintered film; metal powder sintered film; wire mesh ; Or what is formed by combining these is mentioned. Among them, it is preferable to use a plurality of laminated metal fiber nonwoven fabric sintered films from the viewpoint of heat resistance, durability and pressure resistance.

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 still more preferable that it is 5 micrometers or less.

ADVANTAGE OF THE INVENTION According to the resin composition of this invention, it has the outstanding heat resistance and moisture resistance. Moreover, when manufacturing a molded article and a laminated body using the resin composition of this invention, adhesiveness with a shaping|molding roll and releasability are favorable, and even if melt-molding continues for a long period of time, the production|generation of a gel can be improved effectively. Since the molded article and laminated body formed by melt-molding the resin composition according to the present invention have small dimensional changes, few foreign matter defects, and good appearance, they can be suitably used for optical members and the like.

Example

The present invention will be described in more detail with reference to Examples and Comparative Examples below. However, the present invention is not limited to these Examples.

[Resin composition] The physical properties of the methacrylic resin (A) and the resin composition obtained in Production Examples, Examples 1a to 7a and Comparative Examples 1a to 4a were measured by the following methods.

<Glass transition temperature (Tg)>

According to JIS K7121, the temperature at which the resin composition of the present invention is heated from room temperature to 200°C at 20°C/min, held for 10 minutes, cooled to room temperature, and then heated from room temperature to 200°C at 10/min. Differential scanning calorimetry (DSC) analysis was performed for the conditions. The midpoint glass transition temperature calculated|required from the DSC curve measured at the time of the temperature increase of the 2nd time was employ|adopted as the glass transition temperature in this invention. Shimadzu Corporation DSC-50 was used as a measuring apparatus.

<Saturation absorption rate>

Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., SE-180DU-HP), the resin composition of the present invention 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, and a thickness of 2 mm , a square test piece having a side of 50 mm was obtained. The test piece was vacuum-dried on condition of the temperature of 80 degreeC and 5 mmHg for 24 hours. Next, the test piece was left to cool in a desiccator. The test piece was taken out from the desiccator, and the mass (initial mass) was measured immediately.

Next, the test piece was immersed in 23 degreeC distilled water. The test piece was taken out from 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 above. Immersion in distilled water and mass measurement were repeated until the mass change disappeared. From the mass (absorption mass) and the initial mass when the mass change disappeared, the saturated water absorption rate was calculated by the following formula.

Saturated absorption rate (%) = [(absorption mass - initial mass)/initial mass] × 100

<Production Example 1>

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-octylmercaptan, 250 parts by mass of water, 0.09 parts by mass of a dispersant and 1.07 parts by mass of a dispersant. A pH adjuster was added.

While stirring the inside of an autoclave, the liquid temperature was raised from room temperature to 70 degreeC, and it superposed|polymerized by hold|maintaining at 70 degreeC for 120 minute(s). The liquid temperature was lowered to room temperature, and the polymerization reaction liquid was taken out of the autoclave. The solid content was taken out from the polymerization reaction solution by filtration, washed with water, and dried with hot air at 80°C for 24 hours to obtain a bead-like methacrylic resin (A) having a glass transition temperature of 110°C and a saturated water absorption rate of 2.1 mass%.

<Example 1a>

90 parts by mass of methacryl resin (A), 10 parts by mass of vinyl copolymer (B) (manufactured by Denki Chemical Industry Co., Ltd., Regspi R-200, glass transition temperature of 134°C, saturated water absorption of 0.7 mass%) and lubricant (Y) 0.15 parts by mass of cetanol (manufactured by Kao Corporation, Calchol 6098) as a solvent and 0.03 parts by mass of stearic acid monoglyceride (Excel T95, manufactured by Kao Corporation) as a lubricant (x1) were melt-kneaded with a twin-screw kneader at a cylinder temperature of 230°C. Then, the molten resin was extruded and the pellet-form resin composition [1] was obtained. Table 1 shows the composition and physical properties (Tg and saturated water absorption of the resin composition) of the resin composition [1].

<Example 2a>

A resin composition [2] was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 70 parts by mass of the methacrylic resin (A) and 30 parts by mass of the vinyl-based copolymer (B). Table 1 shows the composition and physical properties of the resin composition [2].

<Example 3a>

A resin composition [3] was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 50 parts by mass of the methacrylic resin (A) and 50 parts by mass of the vinyl-based copolymer (B). Table 1 shows the composition and physical properties of the resin composition [3].

<Example 4a>

A resin composition [4] was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 30 parts by mass of the methacrylic resin (A) and 70 parts by mass of the vinyl-based copolymer (B). Table 1 shows the composition and physical properties of the resin composition [4].

<Example 5a>

A resin composition [5] was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 5 parts by mass of the methacrylic resin (A) and 95 parts by mass of the vinyl-based copolymer (B). Table 1 shows the composition and physical properties of the resin composition [5].

<Example 6a>

A resin composition [6] was obtained in the same manner as in Example 4a except that the amount of cetanol was changed to 0.3. Table 1 shows the composition and physical properties of the resin composition [6].

<Example 7a>

A resin composition [7] was obtained in the same manner as in Example 4a except that the amount of stearic acid monoglyceride was changed to 0.05 parts by mass. Table 1 shows the composition and physical properties of the resin composition [7].

<Example 8a>

The resin composition [ 8] The composition and physical properties of the resin composition [8] are shown in Table 1.

<Example 9a>

A resin composition [9] was obtained in the same manner as in Example 4a except that the lubricant (Y) consisting of only 0.15 parts by mass of cetanol was used as the lubricant. Table 1 shows the composition and physical properties of the resin composition [9].

<Example 10a>

A resin composition [10] was obtained in the same manner as in Example 4a except that 0.05 parts by mass of stearyl alcohol (manufactured by Kao Corporation, Calchol 8098) was added as the lubricant (Y). Table 1 shows the composition and physical properties of the resin composition [10].

<Example 11a>

A resin composition [11] was obtained in the same manner as in Example 4a except that stearyl alcohol was used as the lubricant (Y) instead of cetanol. Table 1 shows the composition and physical properties of the resin composition [11].

<Example 12a>

A resin composition [12] was obtained in the same manner as in Example 4a except that stearic acid (manufactured by Kao Corporation, Lunac S-90V) was used as the lubricant (Y) in place of cetanol. Table 1 shows the composition and physical properties of the resin composition [12].

<Example 13a>

A resin composition [13] was obtained in the same manner as in Example 4a except that N,N'-methylenebisstearic acid amide (manufactured by Nippon Chemicals Co., Ltd., bisamide LA) was used as the lubricant (Y) in place of cetanol. Table 1 shows the composition and physical properties of the resin composition [13].

<Example 14a>

A resin composition [14] was obtained in the same manner as in Example 4a except that low-molecular-weight polyethylene (manufactured by Sanyo Chemical Industries, Ltd., Sanwax 15-P) was used as the lubricant (Y) in place of cetanol. Table 1 shows the composition and physical properties of the resin composition [14].

<Comparative Example 1a>

A resin composition [15] was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 95 parts by mass of the methacrylic resin (A) and 5 parts by mass of the vinyl-based copolymer (B). Table 1 shows the composition and physical properties of the resin composition [15].

<Comparative Example 2a>

A resin composition [16] was obtained in the same manner as in Example 1a, except that the composition ratio of the resin mixture (M) was 3 parts by mass of the methacrylic resin (A) and 97 parts by mass of the vinyl-based copolymer (B). Table 1 shows the composition and physical properties of the resin composition [16].

<Comparative Example 3a>

A resin composition [17] was obtained in the same manner as in Example 3a except that the amount of stearic acid monoglyceride serving as the lubricant (x1) was changed to 0.15 parts by mass. Table 1 shows the composition and physical properties of the resin composition [17].

<Comparative Example 4a>

A resin composition [18] was obtained in the same manner as in Example 3a except that a lubricant was not used. Table 1 shows the composition and physical properties of the resin composition [18].

As the above result shows, since the resin composition (Examples 1a - 14a) which concerns on this invention has a high glass transition temperature and a low saturated water absorption, it is excellent in heat resistance and moisture resistance.

[Laminate]

A vented single screw extruder [I] (Toshiba Machinery Co., Ltd.) with a cylinder temperature of 245 to 260° C. and a discharge rate of 430 kg/hour, set to a vented single screw extruder [I] (Sumika Styron Polycarbonate Co., Ltd. “SD Poly”) Car (registered trademark) PCX") pellets were continuously introduced. The pellets of the resin compositions of Examples and Comparative Examples were continuously introduced into a single screw extruder [II] (Toshiba Machinery Co., Ltd.) with a vent having a shaft diameter of 65 mm set at a cylinder temperature of 215 to 230° C. and a discharge amount of 37 kg/hour.

The polycarbonate and the resin composition are simultaneously extruded from the extruder [I] and the extruder [II] and passed through a pleated cylindrical filter (manufactured by Fuji Filter Industries, Ltd.) having a filter pore size of 15 µm each previously filled with resin, followed by a junction block Then, the polycarbonate and the resin composition were co-extruded at a temperature of 230 to 245°C with a multi-manifold die (Nordson Corporation) having a resin outlet width of 1600 mm and a lip spacing of 2.0 mm.

The laminates obtained in Examples 1b to 14b and Comparative Examples 1b to 4b were evaluated by the following method.

<Appearance>

Under the following extrusion conditions, after 15 hours of continuous operation, the obtained laminate was visually observed and the number of defects in the gelatinous foreign matter was counted. A gel-like foreign material defect is a high molecular weight body of the resin composition which showed transparency, and is counted as a defect by disturbing the interface layer of a laminated body. In the area of 2 m<2>, the thing with an average of less than 2 faults was made into Good, and the thing of 2 or more made the thing Poor.

<Formability>

The resin mixture (M) side surface of the laminate was visually observed to examine the presence or absence of a step defect (release mark) orthogonal to the extrusion flow direction. The range of 30 cm in the extrusion flow direction WHEREIN: The thing in which a step-like fault was not visually recognized at all or hardly was made into Good, and the thing which does not correspond to the said Good was made into Poor.

<Amount of warpage change>

From the laminate, a rectangular test piece having a short side of 65 mm and a long side of 110 mm was cut out so that the direction perpendicular to the extrusion flow direction became the short side and the direction parallel to the extrusion flow direction became the long side. The short side of the test piece was picked up and hung, and after leaving it to stand for 4 hours in the environmental tester set to the temperature of 75 degreeC and 50% of relative humidity, as a result of standing to cool the test piece at 25 degreeC, the test piece curved in a gliding motion. Place the test piece curved in a gliding motion on a surface plate so that the end of the test piece is in contact with the surface plate (i.e., the test piece is shaped like a mountain), and the maximum distance between the surface plate and the test piece (usually near the center of the long side of the test piece) maximum) was measured using a gap gauge. This value was made into the initial warpage amount.

Then, the short side of the test piece curved in a sliding motion was picked up and hung, and it was left to stand in the environmental testing machine set to the temperature of 85 degreeC, and 85% of relative humidity for 72 hours. After leaving the test piece to cool for 4 hours in an environmental tester set to 25°C and 50% of relative humidity, the maximum distance between the surface plate and the test piece was measured in the same manner as above. The difference between this measured value and the initial amount of warpage was defined as “the amount of warpage change”. The thing whose warpage change amount was 1.0 mm or less was made into Good, and the thing whose warpage change amount was more than 1.0 mm was made into Poor.

<Scratch resistance>

It measured using the table movable pencil scratching tester (type P) (made by Toyo Seiki Co., Ltd.). The presence or absence of a scratch was confirmed while pressing the lead of a pencil at an angle of 45 degrees and a load of 750 g with respect to the surface of the layer which consists of resin mixture (M) of the laminated body obtained in the Example and the comparative example. The hardness of the pencil lead was increased sequentially, and the hardness of the lead softer by one step from the time point at which a scratch was generated was made scratch resistance. The thing with abrasion resistance made F or more Good, and the thing less than F made it Poor.

<Example 1b>

Pellets of polycarbonate (“SD Polycar (registered trademark) PCX” manufactured by Sumika Styron Polycarbonate Co., Ltd.; the same hereinafter) in a single screw extruder [I] having a shaft diameter of 150 mm set at a cylinder temperature of 245 to 260° C. and a discharge amount of 430 kg/hr. was continuously added. The pellets of the resin composition [1] were continuously injected|thrown-in to the single screw extruder [II] with a shaft diameter of 65 mm set to the cylinder temperature of 215-230 degreeC, and the discharge amount 37 kg/hour.

The polycarbonate and the resin composition [1] were simultaneously extruded from the extruder [I] and the extruder [II], and each passed through a pleated cylindrical filter (manufactured by Fuji Filter Kogyo Co., Ltd.) having a filter pore size of 15 µm which had been previously filled with resin. , introduced into a junction block, and then, polycarbonate and resin composition [1] were co-extruded at a temperature of 245° C. with a multi-manifold die (Nordson Corporation) having a resin outlet width of 1600 mm and a lip spacing of 2.0 mm to form a sheet. did. This sheet is bank-formed between the 1st and 2nd rolls of 4 horizontal rolls, cooled while mirror-transferred with 4 rolls, and a layer made of a resin composition [1] having a thickness of 80 μm and a polycarbonate having a thickness of 920 μm. A laminate having a total thickness of 1000 µm was obtained, which was composed of the layers formed.

<Example 2b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [2], a total thickness of 1000 µm consisting of a layer made of a resin composition [2] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 3b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [3], a total thickness of 1000 µm consisting of a layer made of a resin composition [3] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 4b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [4], a total thickness of 1000 µm consisting of a layer made of a resin composition [4] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 5b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [5], a total thickness of 1000 µm consisting of a layer made of a resin composition [5] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 6b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [6], a total thickness of 1000 µm consisting of a layer made of a resin composition [6] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 7b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [7], a total thickness of 1000 µm consisting of a layer made of a resin composition [7] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 8b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [8], a total thickness of 1000 µm consisting of a layer made of a resin composition [8] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 9b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [9], a total thickness of 1000 µm consisting of a layer made of a resin composition [9] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 10b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [10], a total thickness of 1000 µm consisting of a layer made of a resin composition [10] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 11b>

In the same manner as in Example 1b, except that the resin composition [1] was changed to the resin composition [11], a total thickness of 1000 µm consisting of a layer made of a resin composition [11] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 12b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [12], a total thickness of 1000 µm consisting of a layer made of a resin composition [12] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 13b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [13], a total thickness of 1000 µm consisting of a layer made of a resin composition [13] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Example 14b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [14], a total thickness of 1000 µm consisting of a layer made of a resin composition [14] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Comparative Example 1b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [15], a total thickness of 1000 µm consisting of a layer made of a resin composition [8] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Comparative Example 2b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [16], a total thickness of 1000 µm consisting of a layer made of a resin composition [9] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Comparative Example 3b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [17], a total thickness of 1000 µm consisting of a layer made of a resin composition [9] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

<Comparative Example 4b>

In the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [18], a total thickness of 1000 µm consisting of a layer made of a resin composition [10] having a thickness of 80 µm and a layer made of a polycarbonate having a thickness of 920 µm of the laminate was obtained.

Table 2 shows the evaluation results of Examples 1b to 14b and Comparative Examples 1b to 4b.

As the above results show, it can be seen that the laminates (Examples 1b to 14b) according to the present invention have few defects of foreign substances due to gels, etc., which may be generated during long-term melt molding, and also have few release marks. have. Moreover, it turns out that the laminated body which concerns on this invention is excellent in abrasion resistance, and there is little curvature even if it leaves to stand under high temperature and high humidity.

As uses of the molded article, molded article, and laminated body which concern on this invention, For example, Signboard components, such as an advertising tower, a stand signboard, a protruding signboard, a shop signboard, and a roof signboard; Display parts, such as a showcase, a partition board, and a store display; lighting parts, such as fluorescent lamp covers, mood lighting covers, lamp shades, light ceilings, light walls, and chandeliers; interior parts such as pendants and mirrors; Building parts, such as a door, a dome, a safety window, a partition, a stair board, a balcony board, and the roof of a building for leisure; Transportation aircraft related parts, such as an aircraft windbreak, the visor for pilots, a motorcycle, a motor boat windshield, the shading plate for buses, the side visor for automobiles, a rear visor, a headwing, and a headlight cover; Electronic device parts, such as a nameplate for sound and video, a stereo cover, a television protective mask, and a vending machine display cover; Medical device parts, such as an incubator and a Roentgen part; Instrument related parts, such as a machine cover, an instrument cover, an experiment apparatus, a ruler, a face, and an observation window; Optical related parts, such as a liquid crystal protective plate, a light guide plate, a light guide film, a Fresnel lens, a lenticular lens, the front plate of various displays, and a diffuser plate; Traffic-related parts, such as road signs, information boards, curve mirrors, and soundproof walls; Film members, such as a surface material for automobile interiors, a surface material of a mobile phone, and a marking film; members for household electrical appliances, such as a ceiling material of a washing machine, a control panel, and the ceiling panel of a thermal rice cooker; Other examples include greenhouses, large tanks, box tanks, watch panels, bath stubs, sanitary, desk mats, organic parts, toys, and face protection masks during welding.

This application claims priority on the basis of Japanese Patent Application No. 2015-031222 for which it applied on February 20, 2015, and takes in all the indications here.

Claims (14)

Derived from 5-90 mass % of a methacryl resin (A), a structural unit derived from the aromatic vinyl compound (b1) represented by the following general formula (1), and a cyclic acid anhydride (b2) represented by the following general formula (2) a resin mixture (M) containing 10 to 95 mass% of a vinyl-based copolymer (B) comprising at least a structural unit to
contains a lubricant,
The resin composition in which the said lubricating agent satisfy|fills the following conditions (i) and (ii).
(i) Does not contain a lubricant (x1) comprising monoglycerides of saturated fatty acids having 10 to 24 carbon atoms and a lubricant (x2) comprising a fatty acid ester having two or more hydroxyl groups in one molecule other than the lubricant (x1) .
(ii) higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters (provided that the lubricant (x1) and a lubricant comprising a fatty acid ester having two or more hydroxyl groups in one molecule other than the lubricant (x1) (x2) 0.001 to 2 parts by mass of at least one lubricant (Y) selected from the group consisting of) is contained in an amount of 0.001 to 2 parts by mass based on 100 parts by mass of the resin mixture (M).
[Formula 1]

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group)
[Formula 2]

(R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group) The method of claim 1,
The resin composition wherein the lubricant (Y) is 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 method of claim 1,
The resin composition in which the resin mixture (M) contains 30-60 mass % of a methacrylic resin (A), and 40-70 mass % of a vinyl-type copolymer (B). The method of claim 1,
The vinyl-based copolymer (B) contains 50 to 84 mass% of the structural unit derived from the aromatic vinyl compound (b1), and contains 15 to 49 mass% of the structural unit derived from the cyclic acid anhydride (b2), The resin composition containing 1-35 mass % of structural units derived from methacrylic acid ester (b3). 5. The method of claim 4,
The resin composition whose methacrylic acid ester (b3) is methyl methacrylate. The method of claim 1,
The resin composition whose glass transition temperature is 115-160 degreeC. The method of claim 1,
The resin composition whose saturated water absorption in 23 degreeC water is 0.3-1.9 mass %. The method of claim 1,
A resin composition in which the total amount of the lubricant is 0.1 parts by mass or more with respect to 100 parts by mass of the resin mixture (M). A molded article comprising the resin composition according to any one of claims 1 to 8. A layer comprising the resin composition according to any one of claims 1 to 8;
A laminate comprising a layer comprising a thermoplastic resin composition (T) having a glass transition temperature in the range of 130 to 160°C. 11. The method of claim 10,
A laminate in which the thermoplastic resin composition (T) is a resin composition containing polycarbonate. 11. The method of claim 10,
The laminated body whose difference of the glass transition temperature of a thermoplastic resin composition (T) and the said resin composition is 30 degrees C or less. 11. The method of claim 10,
The laminated body which further equips at least one surface with an abrasion-resistant layer. delete