TW201708372A - Resin composition, molded article and laminate - Google Patents

Abstract

Provided are: a resin composition which contains a methacrylic resin and a lubricant, and which is not susceptible to the formation of a gel during melt molding; and the like. A resin composition according to the present invention contains: a resin mixture (M) that contains a methacrylic resin (A) and a vinyl copolymer (B) containing a structural unit of formula (1) and a structural unit of formula (2); and a lubricant. The lubricant satisfies the following conditions (i) and (ii) with respect to 100 parts by mass of the resin mixture (M). (i) A lubricant (x1) that is composed of a monoglyceride of a saturated fatty acid having 10-24 carbon atoms is not contained, or is contained in an amount of 0.1 part by mass or less. (ii) A lubricant (Y), which is composed of at least one substance selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, metal salts of fatty acids, aliphatic amides and fatty acid esters (excluding lubricants (x1) and lubricants (x2) other than lubricants (x1), which are composed of fatty acid esters that have two or more hydroxyl groups in each molecule), in an amount of 0.001-2 parts by mass. (In general formula (1), each of R1 and R2 independently represents a hydrogen atom or an alkyl group.) (In general formula (2), each of R3 and R4 independently represents a hydrogen atom or an alkyl group).

Description

Resin composition, molded article, and laminate

The present invention relates to a resin composition comprising a methacrylic resin, an ethylene copolymer, and a lubricant. Further, a molded article and a laminate including the resin composition described above.

In the case where the methacrylic resin excellent in transparency, scratch resistance, weather resistance, and the like is contained, the lubricant is contained for the purpose of improving mold release property and workability (for example, Patent Documents 1 and 2). However, physical properties are improved by containing a lubricant, but heat resistance or moisture resistance is lowered. The decrease in heat resistance causes a change in the size of the molded body using the methacrylic resin composition, and thus it is a problem in applications requiring dimensional accuracy. Moreover, the decrease in moisture resistance is also a problem for the same reason.

A copolymer containing styrene and maleic anhydride is known as a resin having high heat resistance and moisture resistance. For example, Non-Patent Document 1 reports a copolymerized resin containing styrene and maleic anhydride containing 18 to 35% by mass of maleic anhydride, and has high heat resistance compared with a methacrylic resin. Further, Non-Patent Document 2 discloses that a copolymer resin of styrene and maleic anhydride is a low water-absorbent resin, and Patent Documents 3 and 4 disclose that it will be included. A copolymerized resin of styrene and maleic anhydride is blended with a composition of a methacrylic resin.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-180454

[Patent Document 2] Japanese Patent No. 3400104

[Patent Document 3] International Publication No. 2014/021264

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2014-160583

[Non-patent literature]

[Non-Patent Document 1] XIRAN (R) SMA "New tricks in polymer blends" [POLYSCOPE] (http://www.bpri.org/documenten/2008_8_flippo.pdf)

[Non-Patent Document 2] 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 the resin composition having improved heat resistance and moisture resistance contains a lubricant and is melt-molded under high temperature conditions, there is a small amount of foreign matter which is polymerized by crosslinking, that is, a gel is formed. It situation. This gel may have a problem of foreign matter defects of the molded article and damage to the appearance of the product.

Further, in a specific application requiring a high-quality appearance, it is filtered by a filter at the time of melt molding, but there is also a problem that gelation is promoted by the filtration. That is, the filter filtration has the effect of capturing and pulverizing the gel which is initially contaminated in the polymerization process such as the polymerization process or the gel which occurs before the filter in the melt forming process, but on the other hand, there is a long-term resin. Staying in the filter contributes to the problem of gelation.

The present invention has been made in view of the above problems, and an object thereof is to provide a resin composition, a molded article, and a laminate which are less likely to form a gel during melt molding in a resin composition containing a methacrylic resin and a lubricant. .

As a result of repeated intensive studies, the inventors of the present invention have found that the above problems can be solved in the following aspects, and the present invention has been completed.

[1] A resin composition comprising a resin mixture (M) and a lubricant, wherein the resin mixture (M) contains 5 to 90% by mass of a methacrylic resin (A), and 10 to 95% by mass of at least The structural unit of the aromatic vinyl compound (b1) represented by the following formula (1) and the ethylene-based copolymer (B) composed of a structural unit derived from the cyclic acid anhydride (b2) represented by the following formula (2) And the lubricant satisfies the following conditions (i) and (ii).

(i) a lubricant (x1) which does not contain a monoglyceride containing a saturated fatty acid having 10 to 24 carbon atoms, or a carbon atom number of 0.1 part by mass or less based on 100 parts by mass of the resin mixture (M) 10~24 saturation a lubricant (x1) of a monoglyceride of a fatty acid; (ii) comprising 0.001 to 2 parts by mass, based on 100 parts by mass of the resin mixture (M), selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, and fats Group of a guanamine and a fatty acid ester (excluding a lubricant (x1) other than the lubricant (x1) and a fatty acid ester having two or more hydroxyl groups in one molecule other than the lubricant (x1)) At least one of the lubricants (Y).

(wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group.)

(wherein R ³ and R ⁴ 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 aliphatic monohydric alcohols having 12 to 18 carbon atoms and saturated fatty acids having 16 to 24 carbon atoms. By.

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

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

[5] The resin composition according to [4], wherein the methacrylate (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 from 0.3 to 1.9% by mass.

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

(iii) a lubricant (x2) containing no lubricant (x2) or 0.1 part by mass or less with respect to 100 parts by mass of the resin mixture (M); (iv) lubricant (x1) and lubricant (x2) The total amount 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 part by mass or more based on 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 layered body comprising a layer composed of the resin composition (C1) according to any one of [1] to [9], and a thermoplastic resin composition having a glass transition temperature of 130 to 160 ° C. (T) The layer formed.

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

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

The resin composition of the present invention exhibits a resin composition capable of forming a gel which is less likely to form a gel during melt forming in a resin composition comprising a methacrylic resin, an aromatic vinyl-cyclic anhydride copolymer, and a lubricant. Excellent effects of molded articles and laminates.

[Formation of the Invention]

Hereinafter, an example of an embodiment applied to the present invention will be described. In addition, the numerical value specific to this specification shows the value obtained by the method as described in the Example mentioned later. For example, the weight average molecular weight Mw and the number average molecular weight Mn are values obtained by a method described in the examples described below by a standard polystyrene equivalent value measured by GPC (gel permeation chromatography). Further, the numerical values "A to B" specific to the present specification indicate values satisfying the numerical value A and greater than the numerical value A, and the numerical value B and the value smaller than the numerical value B.

[Resin composition]

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

(wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group.)

(wherein R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group.)

[Resin Mixture (M)]

The resin mixture (M) of the present invention contains a methacrylic resin (A) and an SMA resin (B).

The content of the methacrylic resin (A) in the resin mixture (M) is in the range of 5 to 90% by mass. The content of the methacrylic resin (A) in the resin mixture (M) is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and most preferably 30% by mass or more. Further, the content of the methacrylic resin (A) in the resin mixture (M) is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass. The mass% or less is preferably 60% by mass or less. The layer containing the resin composition of the present invention is excellent in scratch resistance by the content of the methacrylic resin (A) in the resin mixture (M) of 5% by mass or more, and is 90% by mass. Hereinafter, the occurrence of warpage under high temperature and high humidity can be suppressed when laminating with other layers.

The methacrylic resin (A) is a resin containing a structural unit derived from methacrylate. Examples of the methacrylate include methyl methacrylate (hereinafter referred to as "MMA"), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and methacrylic acid. Butyl ester, isobutyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, bismuth methacrylate An alkyl methacrylate such as an ester, decyl methacrylate or dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, A a cycloalkyl methacrylate such as cyclooctyl acrylate or a tricyclo[5.2.1.0 ^2,6 ]non-8-yl methacrylate; an aryl methacrylate such as phenyl methacrylate; An aralkyl methacrylate such as benzyl acrylate; etc.; from the viewpoint of availability, MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and A are preferred. N-butyl acrylate, isobutyl methacrylate, and butyl methacrylate, preferably MM A. The content of the structural unit derived from the methacrylate in the methacrylic resin (A) is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and may be only from the methyl group. A structural unit of acrylate.

Also, from the viewpoint of heat resistance, methacrylic resin (A) It is preferable to contain 90% by mass or more of the structural unit derived from MMA, more preferably 95% by mass or more, further preferably 98% by mass or more, and it may be a structural unit derived only from MMA.

Further, the methacrylic resin (A) may contain a structural unit derived from a monomer other than methacrylate. For the other monomers, methyl acrylate (hereinafter referred to as "MA"), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate , hexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxy acrylate Butyl ester, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidol acrylate Acrylates such as esters, allyl acrylate, phenyl acrylate, tolyl methacrylate, benzyl acrylate, isodecyl acrylate, 3-dimethylaminoethyl acrylate, etc., from the viewpoint of availability Preferably, it is an acrylate such as MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate or butyl acrylate. More preferably, it is MA and ethyl acrylate. MA. The content of the structural unit derived from the other monomer in the methacrylic resin (A) is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

The methacrylic resin (A) is obtained by polymerizing the above methacrylate alone or by polymerizing a methacrylate with another monomer of any component. In the case of using a plurality of monomers in the polymerization, the monomer mixture is usually mixed after the monomer is mixed to prepare a polymerization. The polymerization method is not particularly limited, but from the viewpoint of productivity, it is preferred to carry out radical polymerization by a method such as a bulk polymerization method, a suspension polymerization method, a solution polymerization method, or an emulsion polymerization method.

The weight average molecular weight (hereinafter referred to as "Mw") of the methacrylic resin (A) is preferably 40,000 to 500,000. When the Mw is 40,000 or more, the layered product of the present invention is excellent in scratch resistance and heat resistance, and the resin mixture (M) is excellent in moldability and the laminate of the present invention is improved by 500,000 or less. Productive.

The content of the SMA resin (B) in the resin mixture (M) is in the range of 10 to 95% by mass. The content of the SMA resin (B) in the resin mixture (M) is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and most preferably 40% by mass or more. In addition, the content of the SMA resin (B) in the resin mixture (M) is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, and most preferably 70% by mass or less. When the content of the SMA resin (B) in the resin mixture (M) is 10% by mass or more, the layer composed of the resin composition of the present invention can be suppressed from high temperature and high humidity when laminated with other layers. The occurrence of warpage is excellent in scratch resistance by being 95% by mass or less.

The SMA resin (B) contains at least an ethylene-based copolymer (B) derived from a structural unit (b1) of an aromatic vinyl compound and a structural unit (b2) derived from a cyclic acid anhydride.

The alkyl group independently represented by R ¹ and R ² in the formula (1) and R ³ and R ⁴ in the formula (2) is preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group. Base, n-butyl, secondary butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, anthracene An alkyl group having a carbon number of 12 or less, such as a group, a decyl group or a dodecyl group, more preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, an isobutyl group or a tertiary group. An alkyl group having a carbon number of 4 or less such as a butyl group.

In the case of R ¹ , a hydrogen atom, a methyl group, an ethyl group and a tertiary butyl group are preferred. R ² , R ³ and R ⁴ are preferably a hydrogen atom, a methyl group or an ethyl group.

The content of the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more. In addition, the content of the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is preferably 84% by mass or less, more preferably 82% by mass or less, still more preferably 80% by mass or less. When the content is in the range of 50 to 84% by mass, the resin mixture (M) is excellent in moisture resistance and transparency. However, in the case where the SMA resin (B) contains two monomers of the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2), the structure derived from the aromatic vinyl compound (b1) in the SMA resin (B) The content of the unit is preferably in the range of 50 to 85% by mass.

The aromatic vinyl compound (b1) may, for example, be styrene; 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tertiary Alkyl-substituted styrene such as butyl styrene or the like; α-alkyl-substituted styrene such as α-methylstyrene or 4-methyl-α-methylstyrene, preferably from the viewpoint of availability It is styrene. These aromatic vinyl compounds (b1) may be used alone or in combination of plural kinds.

The content of the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) is preferably 15% by mass or more, and more preferably 18% by mass or more. Further, it is more preferably 20% by mass or more. In addition, the content of the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) is preferably 49% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less. When the content is in the range of 15 to 49% by mass, the resin mixture (M) is excellent in heat resistance and transparency. However, in the case where the SMA resin (B) contains two monomers of the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2), the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) The content is preferably in the range of 15 to 50% by mass.

The cyclic acid anhydride (b2) may, for example, be maleic anhydride, citraconic anhydride or dimethyl maleic anhydride, and from the viewpoint of availability, maleic anhydride is preferred. The cyclic acid anhydride (b2) may be used singly or in combination of plural kinds.

The SMA resin (B) preferably contains a structural unit derived from a methacrylate in addition to the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2). The content of the structural unit derived from the methacrylate (b3) in the SMA resin (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. In addition, the content of the structural unit derived from the methacrylate (b3) in the SMA resin (B) is preferably 35 mass% or less, more preferably 30 mass% or less, still more preferably 26 mass% or less. When the content is in the range of 1 to 35% by mass, it is possible to further improve transparency and thermal stability.

Examples of the methacrylate (b3) include MMA, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, propyl methacrylate, and methyl group. Isopropyl acrylate, n-butyl methacrylate, isobutyl methacrylate, methyl Tertiary butyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 1-phenylethyl methacrylate, and the like. Among these methacrylates, alkyl methacrylate having a carbon number of 1 to 7 is preferred, and MMA is particularly preferred from the viewpoint of excellent heat resistance and transparency of the obtained SMA resin. Further, the methacrylate may be used singly or in combination of plural kinds.

The SMA resin (B) may have a structural unit derived from an aromatic vinyl compound (b1), a cyclic acid anhydride (b2), and a monomer other than the methacrylate (b3). For the other monomers, it can be listed as MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, hexyl acrylate, acrylic acid 2- Ethylhexyl acrylate, decyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, acrylic acid An acrylate such as phenyl ester, tolyl methacrylate, benzyl acrylate, isodecyl acrylate or 3-dimethylaminoethyl acrylate. These other monomers may be used singly or in combination of plural kinds. In the SMA resin (B), the content of the structural unit derived from the other monomer is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less.

The SMA resin (B) is obtained by polymerizing at least a monomer of the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2). As a monomer, methacrylate (b3) and other monomers of any component can be added to polymerize. . In the polymerization, the monomer mixture is usually prepared by mixing the monomers used in the polymerization. The polymerization method is not particularly limited, but from the viewpoint of productivity, it is preferred to carry out radical polymerization by a method such as a bulk polymerization method or a solution polymerization method.

The Mw of the SMA resin (B) is preferably in the range of 40,000 to 300,000. When the Mw is 40,000 or more, the laminated system of the present invention is excellent in scratch resistance and impact resistance, and the resin mixture (M) is excellent in moldability and the resin composition of the present invention is improved by 300,000 or less. The productivity of the formed molded article.

The mass ratio of the methacrylic resin (A) to the SMA resin (B) contained in the resin mixture (M) (methacrylic resin (A) / SMA resin (B)), from suppressing warpage under high temperature and high humidity The viewpoint of occurrence, transparency, and scratch resistance is preferably in the range of 5/95 to 90/10. The mass ratio is more preferably 10/90 or more, further preferably 15/85 or more, and particularly preferably 20/80 or more. Further, the mass ratio is more preferably 85/15 or less, further preferably 80/20 or less, and particularly preferably 75/25 or less.

For the mixing of the methacrylic resin (A) and the SMA resin (B), for example, a melt mixing method, a solution mixing method, or the like can be used. The melt mixing method uses a melt kneading machine such as a uniaxial or multiaxial kneader, an open roll mill, a Banbury compact kneader, a kneader, or the like, and may be nitrogen, argon, helium or the like as needed. Melt kneading in an inert gas atmosphere. In the solution mixing method, the methacrylic resin (A) and the SMA resin (B) are dissolved and mixed in an organic solvent such as toluene, tetrahydrofuran or methyl ethyl ketone.

The resin mixture (M) may contain a methacrylic resin (A) or a SMA resin (B) insofar as it does not impair the effects of the present invention. Other polymers. Examples of the other polymer include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polypentene, and ethylenically-based ionic polymers; Polystyrene, styrene-maleic anhydride copolymer, impact-resistant polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, styrene resin such as MBS resin; methyl methacrylate- Styrene copolymer; polyester such as polyethylene terephthalate or polybutylene terephthalate; polyamide of nylon 6, nylon 66, polyamine elastomer, etc.; polyphenylene sulfide , polyetheretherketone, polyester, polyfluorene, polyphenylene ether, polyimine, polyetherimide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol Thermoplastic resin such as copolymer or polyacetal; thermosetting resin such as phenol resin, melamine resin, polyoxyxylene resin or epoxy resin; polyvinylidene fluoride, polyurethane, modified polyphenylene ether , polyphenylene sulfide, polyfluorene modified resin; acrylic rubber, polyoxyethylene rubber; styrene thermoplastics such as SEPS, SEBS, SIS, etc. Of the body; IR, EPR, EPDM and other olefin-based rubber and the like. The other polymer may be used singly or in combination of plural kinds.

The content of the other polymer in the resin mixture (M) is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less.

The resin mixture (M) may contain various additives as needed. Examples of the additive include an antioxidant, a thermal deterioration preventive agent, an ultraviolet absorber, a light stabilizer, a lubricant, a mold release agent, a polymer processing aid, an antistatic agent, a flame retardant, a dye/pigment, and the like. Light diffusing agent, matting agent, impact-resistant modifier, phosphor, and the like. The content of such additives may be appropriately set within a range that does not impair the effects of the present invention, as opposed to 100 parts by mass of the resin mixture (M), preferably, for example, the content of the antioxidant is 0.01 to 1 part by mass, the content of the ultraviolet absorber is 0.01 to 3 parts by mass, and the content of the photosetter is 0.01 to 3 parts by mass. The content of the lubricant is set to 0.01 to 3 parts by mass, and the content of the dye/pigment is set to 0.01 to 3 parts by mass.

When the resin mixture (M) contains other polymers and/or additives, it may be added during the polymerization of the methacrylic resin (A) and/or the SMA resin (B), and the methacrylic resin (A) and the SMA resin may be mixed. It may be added at the time of (B), and may be added after mixing the methacrylic resin (A) and the SMA resin (B).

The glass transition temperature of the resin mixture (M) is preferably in the range of from 120 to 160 °C. The lower limit of the glass transition temperature is more preferably 130 ° C or more, and still more preferably 140 ° C or more. Further, the upper limit of the glass transition temperature is more preferably 155 ° C or lower, and still more preferably 150 ° C or lower. By setting the glass transition temperature to a range of 120 to 160 ° C, it is possible to suppress the occurrence of warpage of the molded body composed of the resin composition of the present invention under high temperature and high humidity. In addition, the glass transition temperature in this specification is the temperature computed by the midpoint method using the differential scanning calorimeter, and measuring by the temperature increase rate of 10 degreeC / minute.

The melt flow rate (hereinafter referred to as "MFR") of the resin mixture (M) is preferably in the range of 1 to 10 g/10 minutes. The lower limit of the MFR is more preferably 1.5 g/10 min or more, further preferably 2.0 g/10 min. Further, the upper limit of the MFR is more preferably 7.0 g/10 min or less, further preferably 4.0 g/10 min or less. When the MFR is in the range of 1 to 10 g/10 minutes, the stability of the heat-melt molding is good. In addition, in this manual The MFR of the resin mixture (M) means a value measured using a melt indexer at a temperature of 230 ° C under a load of 3.8 kg.

[lubricant]

The lubricant is a well-known additive added to the resin in order to impart friction reducing property and mold release property. As the lubricant, a higher alcohol-based lubricant, a hydrocarbon-based lubricant, a fatty acid-based lubricant, a fatty acid metal salt-based lubricant, an aliphatic amide-based lubricant, an ester-based lubricant, or the like is known. Among these, the lubricant is used in the present invention to satisfy the following conditions (i) and (ii).

(i) a lubricant (x1) which does not contain a monoglyceride containing a saturated fatty acid having 10 to 24 carbon atoms, or a carbon atom number of 0.1 part by mass or less based on 100 parts by mass of the resin mixture (M) 10~24 lubricant of monoglyceride of saturated fatty acid (x1).

(ii) with respect to 100 parts by mass of the resin mixture (M), it is selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic guanamines, and fatty acid esters (however, the lubricant (x1) and the lubricant The lubricant (Y) of at least one of the group of the lubricant (except for the lubricant (2) containing two or more hydroxyl groups in one molecule other than the agent (x1)) is 0.001 to 2 parts by mass.

The total amount of the lubricant is preferably in the range of 0.001 to 3 parts by mass based on 100 parts by mass of the resin mixture (M), from the viewpoint of the balance between the heat resistance of the resin composition and the appearance quality of the molded article. By setting it in this range, the heat resistance of the resin composition is not remarkably lowered, and the internal slip property of the resin composition is improved, and the metal adhered to the drum, the propeller, the roll, or the like is prevented from coagulating during melt molding such as extrusion molding. On the surface, a molded body having excellent appearance quality is obtained. The total amount of the lubricant is more preferably 0.005 parts by mass or more, further preferably 0.01 parts by mass or more, and further The step is more preferably 0.1 part by mass or more, and most preferably 0.15 part by mass or more. Further, the total amount of the lubricant is more preferably 2 parts by mass or less, still more preferably 1 part by mass or less.

The lubricant (x1) is a lubricant containing a monoglyceride of a saturated fatty acid having 10 to 24 carbon atoms, and the lubricant (x2) is a fatty acid having two or more hydroxyl groups in one molecule in addition to the lubricant (x1). Ester lubricant. In other words, when the lubricant (X) is used as a lubricant containing a fatty acid ester having two or more hydroxyl groups in one molecule, the lubricant (X) includes a lubricant (x1) and a lubricant (x2). The lubricant (x2) is removed from the lubricant (X).

The lubricant (Y) is selected from at least a group comprising a higher alcohol, a hydrocarbon, a fatty acid, a fatty acid metal salt, an aliphatic guanamine, and a fatty acid ester (except for the lubricant (x1) and the lubricant (x2)). One. That is, the lubricant (Y) is a lubricant (X) which is removed from a higher alcohol, a hydrocarbon, a fatty acid, a fatty acid metal salt, an aliphatic guanamine, and a fatty acid ester.

The lubricant (x1) may, for example, be a monoglyceride such as glycerin monostearate or glycerin monodocate. The lubricant (x1) may be used singly or in combination of plural kinds. Further, glycerin monostearate and stearic acid monoglyceride are terms indicating the same compound.

The amount of the lubricant (x1) is 0 to 0.1 part by mass based on 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, still more preferably 0.01 parts by mass or less based on 100 parts by mass of the resin mixture (M). When the amount of the lubricant (x1) is too large, a gel is formed by reacting with the cyclic acid anhydride (b2) unit of the ethylene-based copolymer (B) when the resin composition is melt-molded. However, the molded article tends to cause foreign matter defects or poor appearance.

The lubricant (x2) may, for example, be a polyhydric alcohol fatty acid partial ester other than the lubricant (x1), and specific examples thereof include pentaerythritol monostearate and pentaerythritol distearate. A sorbitan mono/diester such as pentaerythritol mono/diester, sorbitan monostearate or sorbitan monopalmitate.

The lubricant (x2) preferably has a fatty acid having a carbon number of 10 to 40, more preferably 10 to 24, still more preferably 14 to 24. Further, the fatty acid may be an unsaturated fatty acid or a saturated fatty acid. The lubricant (x2) may be used singly or in combination of plural kinds.

The lubricant (Y) is selected from at least a group comprising a higher alcohol, a hydrocarbon, a fatty acid, a fatty acid metal salt, an aliphatic guanamine, and a fatty acid ester (except for the lubricant (x1) and the lubricant (x2)). One. 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 12 to 12 carbon atoms. 18 aliphatic 1 dollar alcohol.

The amount of the lubricant (Y) is 0.001 to 2 parts by mass based on 100 parts by mass of the resin mixture (M). The amount of the lubricant (Y) is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.1 parts by mass or more, and still more preferably 0.12% by mass based on 100 parts by mass of the resin mixture (M). More than one. In addition, the amount of the lubricant (Y) is preferably 1 part by mass or less, and more preferably 0.5 part by mass or less based on 100 parts by mass of the resin mixture (M). When the amount is less than 0.001 parts by mass, the effect of the above lubricant (Y) becomes insufficient, and even if it is more than 2 parts by mass, the further effect of the above lubricant (Y) cannot be obtained, and not only the like, but also such a moist The lubricant oozes out from the molded article to adhere to the surface of the molded article or the like. The lubricant (Y) may be used alone or in combination of two or more. When a plurality of lubricants (Y) having a difference in melting point of 5 ° C or more are used as the lubricant (Y), it is preferable to exhibit an effect of reducing friction or the like in a wider temperature range.

Examples of the above higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and the like. 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, further preferably from the viewpoint of high friction reducing property and less mold contamination or less roller contamination. Further, it is a saturated aliphatic monohydric alcohol having 12 to 18 carbon atoms, and more preferably a saturated aliphatic monohydric alcohol having 16 to 18 carbon atoms.

From the viewpoint of high friction reducing property and high mold release property, the hydrocarbon is preferably an aliphatic hydrocarbon having 12 or more carbon atoms. Further, an aliphatic hydrocarbon such as a liquid paraffin, a microcrystalline wax, a natural paraffin, a synthetic paraffin or a polyolefin wax; a partial oxide of an aliphatic hydrocarbon; or a halogenated compound of an aliphatic hydrocarbon can be used. Even in the case of such a commercially available mixture, the aliphatic hydrocarbon contained 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, eucalyptus acid, tetracosic acid, oleic acid, erucic acid, peanut oleic 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 friction reducing property and less mold contamination or less roller contamination. A number of 16 to 24 saturated fatty acids.

Examples of the fatty acid metal salt include cadmium stearate, cadmium laurate, cadmium ricinoleate, cadmium naphthenate, cadmium 2-ethylhexanoate, strontium stearate, bismuth laurate, strontium ricinoleate. , naphthenate, 2-ethyl Barium hexanoate, calcium stearate, calcium laurate, calcium ricinoleate, barium stearate, zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexanoate, lead stearate, Dibasic lead stearate, lead naphthenate, tin stearate, aluminum stearate, magnesium stearate, and the like.

From the viewpoint of high friction reducing property and low mold contamination or roll contamination, 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. It is a saturated fatty acid with 16 to 24 carbon atoms. From the viewpoint of stability and friction reducing properties, the metal constituting the fatty acid metal salt preferably contains a component selected from the group consisting of calcium, magnesium, zinc, lead, tin, iron, cadmium, aluminum, lanthanum, cobalt, nickel, manganese. At least one metal selected from the group consisting of ruthenium, titanium, vanadium, and copper, more preferably at least one metal selected from the group consisting of calcium, magnesium, zinc, and lead.

Examples of the aliphatic guanamine include decyl laurate, decyl palmitate, decylamine stearate, decylamine aramide, decyl decyl amide, decyl oleate, decyl decanoate, Ammonium succinate, erucamide, decyl methylene bis-stearate, decyl ethyl bis-stearate, and the like. The aliphatic guanamine used in the present invention is preferably a fatty acid decylamine having 12 or more carbon atoms, more preferably a fatty acid decylamine having 16 to 22 carbon atoms, from the viewpoint of high friction reducing property and less mold contamination or less roller contamination. Further, it is preferably an unsaturated fatty acid decylamine having 16 to 22 carbon atoms.

The fatty acid ester (except for the lubricant (x1) + the lubricant (x2)) is a fatty acid ester having no more than two hydroxyl groups in one molecule, and examples thereof include a fatty acid ester of a monohydric alcohol and a dihydric alcohol. Specific examples of the fatty acid esters and the like include diglycerides, triglycerides, acetylated monoglycerides, stearyl stearate, butyl stearate, ethylene glycol monostearate, and B. Glycol Distearate and the like. The fatty acid ester used in the present invention (except for the lubricant (x1) + the lubricant (x2)), the carbon number of the fatty acid in the fatty acid ester from the viewpoint of high friction reducing property and less mold contamination or less roller contamination It is preferably 10 or more, more preferably 16 to 24.

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

(iii) a lubricant (x2) containing no lubricant (x2) or 0.1 part by mass or less with respect to 100 parts by mass of the resin mixture (M); (iv) lubricant (x1) and lubricant (x2) The total amount is in the range of 0 to 0.1 with respect to 100 parts by mass of the resin mixture (M).

In the range which satisfies the condition (iv), the amount of the lubricant (x2) is more preferably 0.05 parts by mass or less, further preferably 0.03 parts by mass or less, based on 100 parts by mass of the resin mixture (M). It is 0.01 parts by mass or less. When the amount of the lubricant (x2) is too large, a gel is formed when the resin composition is melt-molded, which tends to cause foreign matter defects or appearance defects of the molded article.

The resin composition of the present invention may further contain various additives as needed. The additive may, for example, be a thermal stabilizer, an antioxidant, a thermal deterioration preventive agent, an ultraviolet absorber, a light stabilizer, an inorganic filler, an inorganic fiber or an organic fiber, a polymer processing aid, an antistatic agent, or a hard A flammable agent, a dye, a colorant, a matting agent, a light diffusing agent, a tamper-resistant modifier, a phosphor, an adhesive, an adhesion-imparting agent, a plasticizer, a foaming agent, and the like. The content of such additives can be appropriately set within the range not impairing the effects of the present invention. For example, the resin composition 100 of the present invention In the parts by mass, the content of the antioxidant is preferably 0.01 to 1.0 part by mass, the content of the ultraviolet absorber is 0.01 to 3.0 parts by mass, and the content of the dye is set to 0.00001 to 0.01 part by mass.

The preparation method of the resin composition of the present invention is not particularly limited. For example, by kneading the resin mixture (M) at a temperature higher than the softening point, 100 parts by mass of the lubricant (I) and (ii) satisfying the requirements of the resin mixture (M) of the present invention may be added. The blended additive and other polymers are required and obtained by kneading. Further, the resin mixture (M), the lubricant satisfying the requirements (i) and (ii) of the present invention, the additive which can be blended as needed, and other polymer are dissolved in a solvent, and the solvent is removed from the solution. .

The resin composition of the present invention has a glass transition temperature of preferably 115 to 160 °C. More preferably, it is 130 to 155 ° C, and further preferably 140 to 150 ° C. By setting the glass transition temperature of the resin composition in the range of 115 to 160 ° C, the balance of heat resistance and impact resistance of the resin composition is good, for example, the resin composition and a thermoplastic resin such as polycarbonate. The occurrence of warpage of the laminate under high temperature and high humidity is suppressed.

The saturated water absorption of the resin composition of the present invention in water at 23 ° C is preferably from 0.3 to 1.9% by mass. More preferably, it is 0.3 to 1.5% by mass, and further preferably 0.3 to 1.0% by mass. When the saturated water absorption ratio is in the range of 0.3 to 1.9% by mass, warpage of the laminate due to moisture absorption can be suppressed. In addition, the saturated water absorption ratio is a value measured by immersing the molded article in distilled water at 23 ° C and measuring the mass over time, and the mass at the time of reaching equilibrium is increased relative to the mass of the molded article which is vacuum-dried for 3 days or more. rate.

The resin composition of the present invention is subjected to an extrusion molding method such as a co-extrusion molding method, a T-die lamination molding method, or an extrusion coating method; an embedded injection molding method, a two-color injection molding method, a core injection molding method, An injection molding method such as an interlayer injection molding method or a die casting method; a blow molding method; a calender molding method; a press molding method; a method such as a leaching molding method, and a heat-melt molding method, whereby various molded articles can be obtained. Since the resin composition of the present invention is not easily formed into a gel even after long-term melt molding at a high temperature, it is also suitable for producing a molded article requiring high temperature and long-term retention conditions. The resin composition of the present invention is suitable for the production of a thin and wide molded article such as a sheet, a film or a sheet.

[layered body]

The layered system of the present invention has at least one layer composed of the resin composition of the present invention (hereinafter also referred to as a resin composition [C1]) and at least one layer composed of another material. Other materials used in the laminate of the present invention are not particularly limited. For example, an organic material such as a resin; an inorganic material such as a metal monomer or a metal oxide may be mentioned.

The layered system 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 resin composition [C2] of the other layer.

The resin contained in the resin composition [C2] is not particularly limited. Examples of the resin include polyolefins such as polyethylene and polypropylene, polystyrene, (meth)acrylic resins, polyesters, polyamines, polycarbonates, polyvinyl chlorides, and polyvinylidene chlorides. Ethylene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, polyoxymethylene modified resin, polyether ether A ketone, a polybenzazole, a polyphenylene ether, a polyimine, a polyether quinone, a thermosetting resin such as a phenol resin, a melamine resin, a polyoxyxylene resin, or an epoxy resin; an energy ray curable resin. The resin of the resin composition [C2] may be used alone or in combination of two or more. Among these, a thermoplastic resin is preferred, and polycarbonate is more preferred.

When the polycarbonate is used as the resin, the amount of the polycarbonate contained in the resin composition [C2] is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more. The weight average molecular weight of the polycarbonate is preferably from 20,000 to 100,000. When the weight average molecular weight of the polycarbonate is within the above range, the heat resistance and the impact resistance of the resin composition [C2] are improved, and the resin composition can be produced with excellent moldability and high productivity [C1]. A laminated sheet composed of the resin composition [C2]. Further, the Mw/Mn of the polycarbonate is preferably from 1.7 to 2.6, more preferably from 1.7 to 2.3, still more preferably from 1.7 to 2.0.

For the above-mentioned polycarbonate, a commercially available product can be used, and for example, "Caliber (registered trademark)" manufactured by Sumitomo Polycarbonate Co., Ltd., "Iupilon/Novarex (registered trademark)" manufactured by Mitsubishi Engineering Plastics Co., Ltd., "TARFLON (registered trademark)" manufactured by Idemitsu Kosan Co., Ltd., "Panlite (registered trademark)" manufactured by Teijin Chemicals Co., Ltd., etc.

The resin composition [C2] used in the present invention is preferably a thermoplastic resin composition (T) having a glass transition temperature of 130 to 160 °C. The thermoplastic resin composition (T) is preferably a resin composition containing a polycarbonate. Further, the resin composition [C2] is preferably such that the glass transition temperature thereof is the same as the glass transition temperature of the resin composition [C1]. Specifically, resin The difference ΔTg between the glass transition temperature of the composition [C2] and the glass transition temperature of the resin composition [C1] is preferably 30 ° C or lower, more preferably 20 ° C or lower. When the glass transition temperature of the two resins is 30 ° C or less, the effect of suppressing the occurrence of warpage of the laminate under high temperature and high humidity becomes higher.

The resin composition [C2] used in the present invention preferably has a saturated water absorption of 0.2 to 0.5% by mass. Further, the resin composition [C2] preferably has a saturated water absorption ratio which is the same as the saturated water absorption ratio of the resin composition [C1]. Specifically, the difference in saturated water absorption ratio of the resin composition [C2] and the resin composition [C1], that is, the Δ saturated water absorption ratio is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. When the saturated water absorption ratio of the two resins is the same, the effect of suppressing the occurrence of warpage of the laminate under high temperature and high humidity 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. Examples of the additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes, and light diffusing agents. , organic pigments, matting agents, impact-resistant modifiers, phosphors, etc.

The layered system according to another embodiment of the present invention has at least one layer [L1] composed of the resin composition [C1], at least one layer [L2] composed of the resin composition [C2], and at least one layer. Functionality is given to the layer [L3]. The functional imparting layer [L3] is not particularly limited. For example, a scratch-resistant layer, a hard coat layer, an antistatic layer, an antifouling layer, a friction reducing layer, an antiglare layer, an antireflection layer, an adhesive layer, a punching strength imparting layer, and the like can be given. The functional imparting layer [L3] can be formed by a known method. For example, hard coating It can be obtained by applying a resin solution for hard coating, drying and hardening it. 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 functional imparting layers [L3], for example, a scratch-resistant layer, a hard coat layer, an antistatic layer, an antifouling layer, a friction reducing layer, an antiglare layer, an antireflection layer, and the like are usually provided on the outermost side of the laminated body. The functional imparting layer [L3] may be provided in only one type, or a plurality of types may be provided. From the viewpoint of improving the scratch resistance, the laminate of the present invention preferably has a scratch-resistant layer on at least one surface.

The layer constitution in the laminate of the present invention is not particularly limited. In the lamination order of the laminate of the present invention, the layer composed of the resin composition [C1] is marked as the [L1] layer, and the layer composed of the resin composition [C2] is marked as the [L2] layer, and the function is When the property imparting layer [L3] is marked as "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, in the case where the [L3] layer is a hard coat layer, it is preferably [L3] layer / [L1] layer / [L2] layer, [L3] layer / [L1] layer / [L2] layer / [L3] Layer, [L3] layer / [L1] layer / [L2] layer / [L1] layer / [L3] layer.

The present invention is useful in a laminate such as a sheet, a sheet, a film, or the like. In the case where the laminate of the present invention is used as a protective cover, it is preferred to arrange the resin composition [C1] layer on the outermost side when viewed from the protected surface (protected surface). For example, it is preferable to laminate the layer composed of the layer of the [L1] layer/[L2] layer to the [L1] layer/[L2] layer. / The order of the protected surface is configured, or the layered body composed of the layer of the [L1] layer / [L2] layer / [L1] layer is [L1] layer / [L2] layer / [L1] layer / The order of the protective surfaces is configured.

The total thickness of the laminate of the present invention can be set depending on the use, but is preferably 0.2 to 2 mm, more preferably 0.3 to 1.5 mm. When it is too thin, there is a tendency that the rigidity becomes insufficient. When it is too thick, there is a tendency to become a hindrance to weight reduction such as a liquid crystal display device.

The thickness of the layer composed of the resin composition [C1] in the laminate of the present invention is preferably in the range of 0.02 to 0.5 mm. The lower limit of the thickness of the layer is more preferably 0.03 mm or more, further preferably 0.05 mm or more. Further, the upper limit of the thickness of the layer is more preferably 0.3 mm or less, further preferably 0.1 mm or less. When the thickness is less than 0.01 mm, there is a case where the scratch resistance and the weather resistance are insufficient. When it exceeds 0.5 mm, there is a case where the punching resistance is insufficient.

From the viewpoint of suppressing the occurrence of warpage under high temperature and high humidity, the laminated sheet of the present invention preferably has a stacking order as symmetrical in the thickness direction, and more preferably a thickness of each layer becomes symmetrical.

The laminate according to the present invention is not particularly limited by the production method thereof, and can be produced by a multilayer molding method such as multilayer extrusion molding, multilayer blow molding, multilayer pressure molding, multi-color injection molding, or embedded injection molding. . Among these multilayer forming methods, from the viewpoint of productivity, multilayer extrusion molding of the resin composition [C1] and the resin composition [C2] is preferred.

The method of multi-layer extrusion molding is not particularly limited, and a well-known multilayer extrusion molding used for the production of a multilayered laminate of a thermoplastic resin can be employed. The method is formed, for example, by a device having a flat T-die and a polishing roll whose surface has been mirrored. In the case of the T-die, a resin composition [C1] and a resin composition [C2] in a heated molten state may be used as a feed block method or a resin composition which is laminated before flowing into the T-die. The multi-manifold method in which the material [C1] and the resin composition [C2] are laminated inside the T-die. From the viewpoint of improving the smoothness of the interface between the layers constituting the laminate, a multi-manifold method is preferred.

The resin composition [C1] and the resin composition [C2] are preferably melt-filtered by a filter before multilayer molding. By using a plurality of melt-filtered resin compositions to form a plurality of layers, it is possible to obtain a laminated sheet having few defects such as foreign matter and gel. The filter used for the melt filtration is not particularly limited. The filter can be appropriately selected from well-known ones based on the viewpoints such as the use temperature, viscosity, and required filtration accuracy. Specific examples of the filter include non-woven fabrics composed of polypropylene, cotton, polyester, mucilage, glass fiber, etc.; cellulose film impregnated with phenolic resin; sintered metal fiber nonwoven film; sintered metal powder film; metal mesh Or combine these into one. Among them, from the viewpoint of heat resistance, durability, and pressure resistance, it is preferred to use a plurality of laminated metal fiber nonwoven sintered films.

The filtration accuracy of the filter is not particularly limited, but is preferably 30 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less.

The resin composition according to the present invention has excellent heat resistance and moisture resistance. Moreover, when the molded article and the laminated body are produced by using the resin composition of the present invention, the adhesion to the forming roll and the mold release property are good, and the formation of the gel can be effectively improved even if the melt molding is continued for a long period of time. The molded article and the laminated body obtained by melt-molding the resin composition of the present invention have a small dimensional change and a small foreign matter defect, and have a good appearance. Therefore, they can be suitably used for an optical member or the like.

[Examples]

The present invention will be more specifically described below by showing examples and comparative examples. However, the invention is not limited to the embodiments.

[Resin composition]

The physical properties of the methacrylic resin (A) and the resin composition obtained in the 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 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 ° C / min. Under the conditions, differential scanning calorimetry (DSC) was performed. The intermediate point glass transition temperature determined from the DSC curve measured at the second temperature rise was used as the glass transition temperature in the present invention. DSC-50 manufactured by Shimadzu Corporation was used as a measuring device.

<saturated water absorption rate>

The resin composition of the present invention was injection molded using an injection molding machine (SE-180DU-HP, manufactured by Sumitomo Heavy Industries, Ltd.) at 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. Next, the test piece was allowed to cool in a desiccator. The test piece was taken out from the dryer and the mass (initial mass) was measured immediately.

Next, the test piece was immersed in distilled water at 23 °C. The test piece was taken out of the water, the water attached 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. The immersion in distilled water was repeated, and the mass measurement was performed until the quality did not change. The saturated water absorption rate is calculated from the mass (water absorption mass) and the initial mass when the mass is no longer changed by the following formula.

Saturated water absorption (%) = [(water absorption quality - initial quality) / initial quality] × 100

<Manufacturing Example 1>

In the 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, and 250 parts by mass of water were added. 0.09 parts by mass of a dispersant and 1.07 parts by mass of a pH adjuster.

The temperature of the liquid was raised from room temperature to 70 ° C while stirring in the autoclave, and maintained at 70 ° C for 120 minutes to carry out a polymerization reaction. The liquid temperature was lowered to room temperature, and the polymerization reaction liquid was taken out from the autoclave. The solid component was taken out from the polymerization reaction liquid by filtration, washed with water, and dried by hot air at 80 ° C for 24 hours to obtain a bead-like methacrylic resin having a glass transition temperature of 110 ° C and a saturated water absorption ratio of 2.1% by mass [A] .

<Example 1a>

90 parts by mass of methacrylic resin (A) and 10 parts by mass of ethylene-based copolymer (B) were melt-kneaded at a cylinder temperature of 230 ° C using a 2-axis kneading machine (Resistance Co., Ltd., RESISFY R- 200, glass transition temperature 134 ° C, saturated water absorption ratio 0.7 mass%) and 0.15 parts by mass of cetyl alcohol as a lubricant (Y) (KALCOL, manufactured by Kao Co., Ltd.) 6098), 0.03 parts by mass of stearic acid monoglyceride (manufactured by Kao Co., Ltd., EXCEL T95) as a lubricant (x1). Then, the molten resin was extruded to obtain a pelletized resin composition [1]. The composition and physical properties (Tg of the resin composition and saturated water absorption) of the resin composition [1] are shown in Table 1.

<Example 2a>

The resin composition 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 ethylene copolymer (B). . The composition and physical properties of the resin composition [2] are shown in Table 1.

<Example 3a>

A resin composition 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 ethylene copolymer (B). . The composition and physical properties of the resin composition [3] are shown in Table 1.

<Example 4a>

A resin composition 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 ethylene-based copolymer (B). . The composition and physical properties of the resin composition [4] are shown in Table 1.

<Example 5a>

A resin composition 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 ethylene-based copolymer (B). . The composition and physical properties of the resin composition [5] are shown in Table 1.

<Example 6a>

The resin composition [6] was obtained in the same manner as in Example 4a except that the amount of cetyl alcohol was changed to 0.3. The composition and physical properties of the resin composition [6] are shown in Table 1.

<Example 7a>

The 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. The composition and physical properties of the resin composition [7] are shown in Table 1.

<Example 8a>

In addition to replacing stearic acid monoglyceride, 0.03 parts by mass of pentaerythritol distearate (lubricant (x2) (UNISTER H-476D, manufactured by Nippon Oil Co., Ltd.) was added as a lubricant, and The resin composition [8] was obtained in the same manner as in Example 4a. 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 a lubricant (Y) containing only 0.15 part by mass of cetyl alcohol was used as the lubricant. The composition and physical properties of the resin composition [9] are shown in Table 1.

<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 (KALCOL 8098, manufactured by Kao Co., Ltd.) was added as the lubricant (Y). The composition and physical properties of the resin composition [10] are shown in Table 1.

<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) in place of cetyl alcohol. Will tree The composition and physical properties of the lipid composition [11] are shown in Table 1.

<Example 12a>

A resin composition [12] was obtained in the same manner as in Example 4a except that stearic acid (LUNAC S-90V, manufactured by Kao Co., Ltd.) was used as the lubricant (Y) instead of cetyl alcohol. The composition and physical properties of the resin composition [12] are shown in Table 1.

<Example 13a>

A resin was obtained in the same manner as in Example 4a except that N,N'-methylenebisstearic acid decylamine (Bisamide LA, manufactured by Nippon Kasei Co., Ltd.) was used as the lubricant (Y) in place of cetyl alcohol. Composition [13]. The composition and physical properties of the resin composition [13] are shown in Table 1.

<Example 14a>

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

<Comparative Example 1a>

A resin composition 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 ethylene copolymer (B). . The composition and physical properties of the resin composition [15] are shown in Table 1.

<Comparative Example 2a>

A resin composition 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 ethylene-based copolymer (B). . Resin composition The composition and physical properties of the substance [16] are shown in Table 1.

<Comparative Example 3a>

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

<Comparative Example 4a>

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

As shown by the above results, the resin compositions (Examples 1a to 14a) of the present invention are excellent in heat resistance and moisture resistance because of their high glass transition temperature and low saturated water absorption.

[layered body]

In a single-axis extruder [I] (Toshiba Machinery Co., Ltd.) with a vent hole of 150 mm in diameter and a discharge volume of 430 to 260 ° C and a discharge capacity of 430 kg / hour, polycarbonate was continuously supplied ( A pellet of "SD POLYCA (registered trademark) PCX" manufactured by Styron Polycarbonate Co., Ltd.). In the single-axis extruder [II] (Toshiba Machine Co., Ltd.) with a venting hole with a shaft diameter of 65 mm set to a barrel temperature of 215 to 230 ° C and a discharge rate of 37 kg / hour, the examples and comparisons were continuously input. For example, the pellet of the resin composition.

Simultaneously extruding the polycarbonate and resin composition from the extruder [I] and the extruder [II], respectively, through a pre-filled resin filter hole size of 15 μm folding cylinder filter (Fuji Filter Industry Co., Ltd. After the company system), the junction block was introduced, and the polycarbonate was extruded at a temperature of 230 to 245 ° C in a multi-manifold mold (Nordson Co., Ltd.) having a resin discharge opening width of 1600 mm and a lip interval of 2.0 mm. With resin composition.

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

<Appearance>

Among the extrusion conditions described below, the laminate obtained after continuous operation for 15 hours was visually observed and the number of gel-like foreign matter defects was counted. The gelled foreign matter defect refers to a high molecular weight body of a resin composition exhibiting transparency, which is disturbed by disturbing the interface layer of the laminate. In an area of 2 m ² , it is preferable that the number of defects is less than two on average, and that two or more are Poor.

<formability>

The side surface of the resin mixture (M) of the laminate was visually observed, and the presence or absence of a stepped defect (release impression) orthogonal to the direction of the extrusion flow was examined. In the range of 30 cm in the direction of the extrusion flow, it is preferable that the stepped defects are all or substantially undetectable, and Poor is not in conformity with the aforementioned Good.

<Amount of warpage change>

The rectangular test piece having a short side of 65 mm and a long side of 110 mm was cut out from the laminated body so that the direction perpendicular to the direction of the extrusion flow became the short side and the direction parallel to the direction of the extrusion flow became the long side. The short side of the suspended test piece was placed in an environmental tester set to a temperature of 75 ° C and a relative humidity of 50%, and after standing for 4 hours, the test piece was allowed to cool to 25 ° C, and the test piece was bent into a bow shape. The test piece bent into an arch shape is placed on the platform in such a manner that the end of the test piece contacts the platform (that is, in such a manner that the test piece is in the shape of a mountain), and the test piece and the test piece are measured using a feeler gauge. The maximum distance between the gaps (usually the maximum value near the center of the long side of the test piece). This value is taken as the initial warpage amount.

Next, the short side of the test piece which was bent and arched was placed in an environmental tester set to a temperature of 85 ° C and a relative humidity of 85% for 72 hours. After the test piece was allowed to cool in an environmental tester set to 25 ° C and a relative humidity of 50% for 4 hours, the maximum distance between the space between the stage and the test piece was measured in the same manner as above. The difference between this measured value and the initial warpage amount is defined as "the amount of warpage change". It is good if the amount of warpage change is 1.0 mm or less, and Poor if the amount of warpage change exceeds 1 mm.

<scratch resistance>

It was measured using a table-top mobile pencil scratch tester (type P) (made by Toyo Seiki Co., Ltd.). With respect to the surface of the layer of the resin mixture (M) including the laminate obtained in the examples and the comparative examples, the core of the pencil was pressed at an angle of 45 degrees and a load of 750 g, and the presence or absence of scratches was confirmed. The hardness of the core of the pencil is gradually increased, and the hardness of the core of the first stage is softer than the time at which the scratch is generated. Those having a scratch resistance of F or more are preferred, and those less than F are poor (Poor).

<Example 1b>

In a uniaxial extruder [I] set to a cylinder temperature of 245 to 260 ° C and a discharge capacity of 430 kg / hr, a diameter of 150 mm was continuously supplied to polycarbonate (SD POLYCA, manufactured by Storon Polycarbonate Co., Ltd.). Registered trademark) PCX". The same as the following pellets. The pellet of the resin composition [1] was continuously introduced into a uniaxial extruder [II] set to a cylinder temperature of 215 to 230 ° C and a discharge amount of 37 kg / hour and a shaft diameter of 65 mm.

Simultaneous extrusion of polycarbonate and resin composition [1] from extruder [I] and extruder [II], respectively, through a pre-filled resin filter hole size 15 μm folding cylinder filter (Fuji filter industry After the joint making process, the joint was introduced, and the polycarbonate and the resin composition were heated at a temperature of 245 ° C in a multi-manifold mold (Nordson Co., Ltd.) having a resin discharge opening width of 1600 mm and a lip interval of 2.0 mm [1]. Coextruded to form a sheet. This sheet was bank-formed between the first and second rolls of the four rolls in the lateral direction, and cooled by transferring the mirror surface with four rolls to obtain a resin composition [1] having a thickness of 80 μm. The layer was laminated with a total thickness of 1000 μm of a layer made of polycarbonate having a thickness of 920 μm.

<Example 2b>

A layer composed of the resin composition [2] and a polycarbonate having a thickness of 920 μm having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [2]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 3b>

A layer composed of the resin composition [3] and a thickness of 920 μm including polycarbonate having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [3]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 4b>

A layer composed of the resin composition [4] and a thickness of 920 μm including polycarbonate having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [4]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 5b>

A layer composed of the resin composition [5] and a polycarbonate having a thickness of 920 μm having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [5]. The layer is composed of a laminate having a total thickness of 1000 μm.

<Example 6b>

A layer composed of the resin composition [6] and a thickness of 920 μm including polycarbonate having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [6]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 7b>

A layer composed of the resin composition [7] and a thickness of 920 μm including polycarbonate having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [7]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 8b>

A layer composed of the resin composition [8] and a thickness of 920 μm including polycarbonate having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [8]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 9b>

A layer composed of the resin composition [9] and a polycarbonate having a thickness of 920 μm having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [9]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 10b>

A layer composed of the resin composition [10] and a polycarbonate having a thickness of 920 μm having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [10]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 11b>

A layer composed of the resin composition [11] and a thickness of 920 μm including polycarbonate having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [11]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 12b>

A layer composed of the resin composition [12] and a polycarbonate having a thickness of 920 μm, which had a thickness of 80 μm, were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [12]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 13b>

A layer composed of the resin composition [13] and a thickness of 920 μm including polycarbonate having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [13]. A layered body having a total thickness of 1000 μm of the layer formed.

<Example 14b>

A layer composed of the resin composition [14] and a thickness of 920 μm including polycarbonate having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [14]. A layered body having a total thickness of 1000 μm of the layer formed.

<Comparative Example 1b>

A layer composed of the resin composition [8] and a thickness of 920 μm including polycarbonate having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [15]. A layered body having a total thickness of 1000 μm of the layer formed.

<Comparative Example 2b>

A layer composed of a resin composition [9] and a thickness of 920 μm and having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [16]. The layer has a total thickness of 1000 μm.

<Comparative Example 3b>

A layer composed of the resin composition [9] and a polycarbonate having a thickness of 920 μm having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [17]. A layered body having a total thickness of 1000 μm of the layer formed.

<Comparative Example 4b>

A layer composed of the resin composition [10] and a thickness of 920 μm including polycarbonate having a thickness of 80 μm were obtained in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [18]. A layered body having a total thickness of 1000 μm of the layer formed.

The evaluation results of Examples 1b to 14b and Comparative Examples 1b to 4b are shown in Table 2.

As shown in the above results, it is known that the laminates of the present invention (Examples 1b to 14b) are less likely to have foreign matter defects such as gels generated during melt molding for a long period of time, and have less mold release marks. Furthermore, this hair is known The laminate of the bright layer is excellent in scratch resistance and has little warpage even when placed under high temperature and high humidity.

[Industrial availability]

Examples of the use of the molded article, the molded article, and the laminated body of the present invention include: advertising towers, standing signboards, side signboards, door signs, roof signboards, and the like; display cabinets, partition boards Display parts such as shop displays; fluorescent lamp shades, atmosphere lighting shades, lampshades, illuminated ceilings, light walls, chandeliers, etc.; decorative parts such as pendants, mirrors, etc.; doors, vaults, safety glass windows, partition walls, stair protection walls Building parts such as balcony walls and roofs for leisure buildings; aircraft windshield, pilot sun visor, motorcycle, motorboat windshield, bus visor, car sun visor, rear sun visor, front wing, front Parts related to transportation such as lampshade; electronic equipment parts such as signage for sound image, stereo casing, TV protection mask, vending machine display cover; medical equipment parts such as incubator and X-ray parts; mechanical casing and instrument cover, Machine-related parts such as experimental devices, scales, dials, observation windows, etc.; liquid crystal protective plates, light guide plates, light guiding films, Philippine Optical related parts such as ear lenses, lenticular lenses, front panels of various displays, diffusers, etc.; traffic-related parts such as road signs, guide plates, curved mirrors, and soundproof walls; surface materials for automotive interiors, mobile phone surface materials, marking films, etc. Thin film member; upper cover material of washing machine and control panel, top panel of rice cooker and other components for home appliances; other, greenhouse, large sink, box-shaped sink, clock panel, bathtub, sanitary equipment, table mat, game parts , toys, masks for face protection during welding, etc.

Claims (14)

A resin composition comprising a resin mixture (M) and a lubricant, the resin mixture (M) comprising 5 to 90% by mass of a methacrylic resin (A), and 10 to 95% by mass of at least the following The structural unit of the aromatic vinyl compound (b1) represented by the formula (1) and the ethylene-based copolymer (B) derived from the structural unit of the cyclic acid anhydride (b2) represented by the following formula (2), the lubrication The agent satisfies the following conditions (i) and (ii): (i) a lubricant (x1) containing no monoglyceride containing a saturated fatty acid having 10 to 24 carbon atoms, or a resin mixture (M) 100 The lubricant (x1) containing 0.1% by mass or less of a monoglyceride of a saturated fatty acid having 10 to 24 carbon atoms; (ii) 0.001 to 100 parts by mass of the resin mixture (M); 2 parts by mass of a compound containing a higher alcohol, a hydrocarbon, a fatty acid, a fatty acid metal salt, an aliphatic decylamine, and a fatty acid ester (wherein the lubricant (x1) and the lubricant (x1) are contained in one molecule) Lubricant (Y) of at least one of the group of two or more hydroxyl fatty acid ester lubricants (except for x2), (wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group); (wherein R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group). The resin composition of claim 1, 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 resin composition of claim 1 or 2, wherein the resin mixture (M) contains 30 to 60% by mass of the methacrylic resin (A) and 40 to 70% by mass of the ethylene-based copolymer (B). The resin composition of claim 1 or 2, wherein the ethylene-based copolymer (B) contains 50 to 84% by mass of a structural unit derived from the aromatic vinyl compound (b1), and contains 15 to 49% by mass of a cyclic acid anhydride. The structural unit of (b2) contains 1 to 35% by mass of a structural unit derived from methacrylate (b3). The resin composition of claim 4, wherein the methacrylate (b3) is methyl methacrylate. The resin composition of claim 1 or 2, wherein the glass transition temperature is 115 to 160 °C. The resin composition of claim 1 or 2, wherein the saturated water absorption in water at 23 ° C is from 0.3 to 1.9% by mass. The resin composition of claim 1 or 2, wherein the lubricant further satisfies the following conditions (iii) and (iv): (iii) no lubricant (x2), or 100 mass relative to the resin mixture (M) a part of the lubricant (x2) of 0.1 part by mass or less; (iv) The total amount of the lubricant (x1) and the lubricant (x2) is in the range of 0 to 0.1 part by mass based on 100 parts by mass of the resin mixture (M). The resin composition of claim 1 or 2, wherein the total amount of the lubricant is 0.1 part by mass or more based on 100 parts by mass of the resin mixture (M). A molded article comprising the resin composition according to any one of claims 1 to 9. A layered product comprising a layer composed of the resin composition according to any one of claims 1 to 9 and a layer composed of a thermoplastic resin composition (T) having a glass transition temperature of 130 to 160 °C. The laminate according to claim 11, wherein the thermoplastic resin composition (T) is a resin composition containing a polycarbonate. The laminate according to claim 11 or 12, wherein a difference in glass transition temperature between the thermoplastic resin composition (T) and the resin composition is 30 ° C or lower. The laminate according to claim 11 or 12 further comprising a scratch-resistant layer on at least one surface.