KR20180041616A - Resin composition, molded article and laminate - Google Patents

Abstract

[PROBLEMS] To provide a resin composition having high transparency and high surface hardness, chemical resistance and glass transition temperature. Also provided are a molded article and a laminate using the resin composition.
(1) A thermoplastic resin composition comprising 5 to 90% by mass of a methacrylic resin (A) containing 99% by mass or more of a structural unit derived from methyl methacrylate and an aromatic vinyl compound (b1) represented by at least the following general formula And 10 to 95% by mass of a vinyl copolymer (B) comprising a structural unit derived from a cyclic acid anhydride (b2) represented by the following general formula (2). (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)

Description

RESIN COMPOSITION, MOLDED ARTICLE AND LAMINATE [0002]

The present invention relates to a resin composition comprising a methacrylic resin and a vinyl-based copolymer. The present invention also relates to a molded article and a laminate containing the resin composition.

A methacrylic resin excellent in transparency, scratch resistance and weather resistance is useful as a material for a molded article used for an optical member, an illuminating member, a signboard member, a decorative member, and the like. However, since the methacrylic resin has a low glass transition temperature of about 110 占 폚, the molded article made of the resin is liable to be deformed by heat.

As a method for increasing the glass transition temperature of a methacrylic resin, there is known a method of polymer blending a copolymer resin (SMA resin) comprising styrene and maleic anhydride in a methacrylic resin. For example, in Non-Patent Document 1, various polymer blends of various SMA resins having different copolymerization ratios of methacrylic resin and maleic anhydride are studied, and SMA resin containing 8 to 33 mass% of maleic anhydride is referred to as meta Has been reported to have a high glass transition temperature in comparison with a methacrylic resin in common with a cresylic resin. Further, in Patent Document 1, it has been reported that a polymer blend of a copolymer comprising styrene, maleic anhydride and methyl methacrylate and a methacrylic resin has a high glass transition temperature and low water absorption. Patent Document 2 discloses a laminate comprising a layer made of a resin composition containing a methacrylic resin and an SMA resin and a layer made of polycarbonate.

Japanese Laid-Open Patent Publication No. 2015-105371 International Publication No. 2015/050051

 C. R. BRANNOC K, J. W. BARLOW, and D. R. PAUL, Journal of Polymer Science: Part B: Polymer Physics, Vol. 29, 413-429 (1991)

However, the resin composition obtained by this method has a problem that the surface hardness and chemical resistance are lowered due to the influence of the SMA resin. By reducing the composition ratio of the SMA resin, deterioration of the surface hardness and chemical resistance can be suppressed, but the glass transition temperature of the resulting resin composition becomes insufficient.

The present invention has been made in view of the above problems. It is an object of the present invention to provide a resin composition containing a methacrylic resin and an SMA resin and having a high surface hardness, a high chemical resistance and a high glass transition temperature without deteriorating the high transparency characteristic of the methacrylic resin, To provide a molded article and a laminate.

As a result of intensive research conducted by the present inventors, it has been found out that the above-mentioned problems can be solved in the following embodiments, and the present invention has been accomplished.

[1] A thermoplastic resin composition which comprises 5 to 90% by mass of a methacrylic resin (A) containing 99% by mass or more of a structural unit derived from methyl methacrylate and 5 to 90% by mass of an aromatic vinyl compound (b1) And 10 to 95% by mass of a vinyl copolymer (B) comprising a structural unit and a structural unit derived from a cyclic acid anhydride (b2) represented by the following general formula (2).

[Chemical Formula 1]

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

(2)

(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 methacrylic resin (A) contains 99.5% by mass or more of a structural unit derived from methyl methacrylate.

[3] The resin composition according to [1] or [2], wherein the methacrylic resin (A) has a syndiotacticity (rr) of not less than 50% in a triplet notation.

[4] The resin composition according to any one of [1] to [3], which contains 30 to 60% by mass of a methacrylic resin (A) and 40 to 70% by mass of a vinyl copolymer (B).

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

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

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

[8] The resin composition according to any one of [1] to [7], which contains an ultraviolet absorber.

[9] The resin composition according to [8], wherein the ultraviolet absorber has a benzotriazole skeleton.

[10] The resin composition according to [9], wherein the ultraviolet absorber has a triazine skeleton.

[11] The resin composition according to any one of [8] to [10], wherein the ultraviolet absorber contains sulfur in its skeleton.

[12] The resin composition according to any one of [8] to [11], which contains two or more ultraviolet absorbers.

[13] A molded article comprising the resin composition according to any one of [1] to [12].

[14] A laminate comprising a layer made of the resin composition according to any one of [1] to [12] and a thermoplastic resin composition (T) having a glass transition temperature in the range of 130 to 160 ° C.

[15] The laminate according to [14], wherein the thermoplastic resin composition (T) is a resin composition containing polycarbonate.

[16] A laminate according to [14] or [15], wherein the absolute value of the difference between the thermoplastic resin composition (T) and the Tg of the resin composition is 30 캜 or less.

[17] The laminate according to any one of [14] to [16], further comprising a scratch-resistant layer on at least one surface of the laminate.

The resin composition according to the present invention is a resin composition which contains a methacrylic resin and an SMA resin and which has a high surface hardness, a high chemical resistance and a high glass transition temperature without deteriorating the high transparency characteristic of the methacrylic resin, And can provide a molded article and a laminate comprising the same.

Hereinafter, an example of an embodiment to which the present invention is applied will be described. The numerical values specified in the present specification indicate values obtained by the methods described in the following examples. For example, the weight average molecular weight Mw is a standard polystyrene-reduced value measured by GPC (gel permeation chromatography) and is a value obtained by the method described in Examples described later. The numerical values " A to B " specified in the present specification indicate a range which is larger than the numerical value A and the numerical value A and which is smaller than the numerical value B and the 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) (Hereinafter referred to as " SMA resin (B) ") containing a structural unit derived from a vinyl monomer (B).

(3)

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

[Chemical Formula 4]

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

The content of the methacrylic resin (A) in the resin composition of the present invention is in the range of 5 to 90% by mass. The content of the methacrylic resin (A) in the resin composition is preferably 10 mass% or more, more preferably 15 mass% or more, further preferably 20 mass% or more, and most preferably 30 mass% or more. The content of the methacrylic resin (A) in the resin composition is preferably 85% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and most preferably 60% by mass or less. The layer made of the resin composition of the present invention is excellent in scratch resistance because the content of the methacrylic resin (A) in the resin composition is 5 mass% or more, and is 90 mass% or less. When the layer is laminated with other layers, It is possible to suppress the occurrence of warping in the case of the present invention.

The methacrylic resin (A) has a structural unit derived from methyl methacrylate (hereinafter referred to as " MMA ") in an amount of 99 mass% or more, preferably 99.5 mass% or more, and more preferably 100 Mass%. When the methacrylic resin (A) contains 99 mass% or more of structural units derived from MMA, the heat resistance and chemical resistance of the resin composition of the present invention can be enhanced. The content of the structural unit derived from MMA of the methacrylic resin (A) is determined by pyrolysis gas chromatography and thermal decomposition and volatile component separation of the resin purified by reprecipitation of the methacrylic resin (A) in methanol , And can be calculated from the ratio of the peak area of the obtained MMA and the copolymerization component (mainly methyl acrylate).

The methacrylic resin (A) contained in the resin composition of the present invention may contain not more than 1% by mass of a structural unit derived from a monomer other than MMA in the whole monomer unit, but preferably contains no structural unit Do.

As the monomer, a structural unit derived from methacrylic acid ester other than MMA may be mentioned. Examples of such methacrylic esters include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate Methacrylic acid alkyl esters such as hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, methanyloxanyl, decyl methacrylate, and decyl dodecyl methacrylate; Methacrylic acid such as 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, and tricyclo [5.2.1.0 ^2,6 ] deca-8-methacrylate Cycloalkyl esters; Methacrylic acid aryl esters such as phenyl methacrylate; Methacrylic acid aralkyl esters such as benzyl methacrylate; And the like. From the viewpoint of availability, preferred are ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate. The content of the structural units derived from methacrylic acid esters other than MMA in the methacrylic resin (A) is preferably 1% by mass or less, more preferably 0.5% by mass or less, in total, and the content of the structural units derived from methacrylic acid And most preferably does not contain an ester-derived structural unit.

As the above-mentioned monomers, structural units derived from monomers other than methacrylic acid esters can be mentioned. 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- Ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate Methacryloxypropyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, tolyl acrylate, benzyl acrylate, isobornyl acrylate, Acrylic acid esters such as dimethylaminoethyl, and from the viewpoint of availability, MA, ethyl acrylate, n-propyl acrylate, Acrylic acid esters such as isopropyl acrylate, n-butyl acrylate, isobutyl acrylate and tert-butyl acrylate are preferable, MA and ethyl acrylate are more preferable, and MA is most preferable. The content of the structural units derived from these other monomers in the methacrylic resin (A) is preferably 1% by mass or less, more preferably 0.5% by mass or less, in total, and the content of structural units derived from other monomers other than methacrylic acid ester And most preferably does not contain a structural unit derived from

The methacrylic resin (A) is obtained by polymerizing MMA alone or another monomer as an optional component. When a plurality of kinds of monomers are used in such polymerization, usually, these plural kinds of monomers are mixed to prepare a monomer mixture, and then the mixture is provided for polymerization. The polymerization method is not particularly limited, but from the viewpoint of productivity, radical polymerization is preferably carried out by a bulk polymerization method, a suspension polymerization method, a solution polymerization method, an emulsion polymerization method or the like.

The methacrylic resin (A) preferably has a lower limit of syndiotacticity (rr) in the triplet display of 50% or higher, more preferably 51% or higher, and still more preferably 52% or higher. Since the lower limit of the content of such a structure is 50% or more, the resin composition of the present invention is excellent in heat resistance.

Herein, the syndiotacticity rr of the triplet display (hereinafter sometimes simply referred to as " syndiotacticity (rr) ") is a value obtained by subtracting 2 It is the ratio of the two chains (diad) together, which is la salmo (denoted rr). In the chain of the structural units (two consecutive diad) in the polymer molecule, the same three-dimensional configuration is referred to as meso, while the opposite one is referred to as racemo and denoted by m and r, respectively.

The syndiotacticity (rr) (%) of the methacrylic resin (A) was determined by measuring the ¹ H-NMR spectrum at 30 ° C in deuterated chloroform and measuring the tetramethylsilane (TMS) (X / Y) x 100, by measuring the area (X) of the area of 0.6 to 0.95 ppm and the area (Y) of the area of 0.6 to 1.35 ppm when measured.

The weight average molecular weight (hereinafter referred to as "Mw") of the methacrylic resin (A) is preferably 40,000 to 500,000, more preferably 60,000 to 300,000, and even more preferably 80,000 to 200,000. By having the Mw of 40,000 or more, the resin composition of the present invention has excellent mechanical strength, and when it is 500,000 or less, the compatibility with the SMA resin is improved and the transparency of the molded article made of the resin composition of the present invention can be enhanced.

The glass transition temperature of the methacrylic resin (A) is preferably 100 占 폚 or higher, more preferably 105 占 폚 or higher, and even more preferably 110 占 폚 or higher. Since the glass transition temperature is 100 占 폚 or higher, the resin composition of the present invention has excellent heat resistance. In the present specification, the glass transition temperature is a temperature measured by a differential scanning calorimeter at a temperature raising rate of 10 ° C / min and calculated by a gravimetric method.

The saturated water absorption rate of the methacrylic resin (A) in water at 23 캜 is preferably 2.5 mass% or less, more preferably 2.3 mass% or less, and further preferably 2.1 mass% or less. When the saturated water absorption rate is 2.5% by mass or less, the resin composition of the present invention is excellent in moisture resistance, and warpage of the laminate resulting from moisture absorption can be suppressed. The saturated water absorption rate in the present specification means the mass of the molded article vacuum-dried 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 As the rate of increase.

The melt flow rate (hereinafter referred to as " MFR ") of the methacrylic resin (A) is preferably in the range of 1 to 10 g / 10 min. The lower limit value of the MFR is more preferably 1.2 g / 10 min or more, and further preferably 1.5 g / 10 min. The upper limit of the MFR is more preferably 7.0 g / 10 min or less, and further preferably 4.0 g / 10 min or less. When the MFR is in the range of 1 to 10 g / 10 min, the stability of hot melt molding is good. The MFR of the resin composition of the present invention in the present specification is a value measured under a load of 230 캜 and a load of 3.8 ㎏ using a melt indexer.

The content of the SMA resin (B) in the resin composition of the present invention is in the range of 10 to 95 mass%. The content of the SMA resin (B) in the resin composition is preferably 15 mass% or more, more preferably 20 mass% or more, further preferably 25 mass% or more, and most preferably 40 mass% or more. The content of the SMA resin (B) in the resin composition is preferably 90 mass% or less, more preferably 85 mass% or less, even more preferably 80 mass% or less, and most preferably 70 mass% or less. The laminate of the present invention can suppress the occurrence of warpage under high temperature and high humidity when it is laminated with another layer because the content of the SMA resin (B) in the resin composition is 10 mass% or more, and is 95 mass% or less Excellent scratch resistance.

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 represented by R ¹ and R ^{2 in} the general formula (1) and R ³ and R ⁴ in the general formula (2) independently include a methyl group, ethyl group, n-propyl group, isopropyl group, propyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- , A decyl group and a dodecyl group are preferable and an alkyl group having 12 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec- More preferably an alkyl group having 4 or less carbon atoms.

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% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more. 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, and even more preferably 80% by mass or less. When the content is in the range of 50 to 84 mass%, the resin composition of the present invention is excellent in moisture resistance and transparency. However, when the SMA resin (B) is composed of only two monomers, the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2), the content of the structural unit derived from the aromatic vinyl compound (b1) The content is preferably in the range of 50 to 85% by mass.

Examples of the aromatic vinyl compound (b1) include styrene; Substituted styrenes such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene and 4-tert-butylstyrene; ? -alkyl substituted styrene such as? -methyl styrene and 4-methyl-? -methyl styrene; And styrene is preferable from the standpoint of availability. These aromatic vinyl compounds (b1) may be used singly or in combination.

The content of the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) is preferably at least 15 mass%, more preferably at least 18 mass%, further preferably at least 20 mass%. 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 mass%, the resin composition of the present invention is excellent in heat resistance and transparency. When the SMA resin (B) is composed of only two monomers, 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 Is preferably in the range of 15 to 50 mass%.

Examples of the cyclic acid anhydride (b2) include maleic anhydride, citraconic anhydride, and 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.

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

Examples of the methacrylic acid ester (b3) include MMA, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, propyl methacrylate, isopropyl methacrylate, Butyl methacrylate, t-butyl methacrylate, t-butyl butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 1-phenylethyl methacrylate; And the like. Among these methacrylic acid esters, methacrylic acid alkyl ester having 1 to 7 carbon atoms in the alkyl group is preferable, and MMA is particularly preferable because the obtained SMA resin is excellent in heat resistance and transparency. The methacrylic esters may be used alone or in combination of two or more.

The SMA resin (B) may have a structural unit derived from a 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 monomers such as MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, Stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, Acrylic acid esters such as methyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, tolyl acrylate, benzyl acrylate, isobornyl acrylate and 3-dimethylaminoethyl acrylate. have. One of these other monomers may be used alone, or a plurality of these monomers may be used in combination. The content of the structural unit derived from such another monomer in the SMA resin (B) 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 monomers of at least an aromatic vinyl compound (b1) and a cyclic acid anhydride (b2). As the monomer, a methacrylic acid ester (b3) and another monomer as an optional component may be added and polymerized. In such polymerization, usually, the monomers to be used are mixed to prepare a monomer mixture, which is then supplied to polymerization. The polymerization method is not particularly limited, but from the viewpoint of productivity, radical polymerization is preferably carried out by a bulk polymerization method, a solution polymerization method or the like.

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 resin composition of the present invention has excellent mechanical strength, and when it is 300,000 or less, the compatibility with the methacrylic resin becomes good and the transparency of the molded article made of the resin composition of the present invention can be enhanced .

The glass transition temperature of the SMA resin (B) is preferably 115 占 폚 or higher, more preferably 120 占 폚 or higher, and even more preferably 125 占 폚 or higher. With such a glass transition temperature of 110 占 폚 or higher, the resin composition of the present invention has excellent heat resistance and can suppress the warpage of the laminate caused by heat.

The saturation absorption rate of the SMA resin (B) in water at 23 캜 is preferably 1.0 mass% or less, more preferably 0.8 mass% or less, and still more preferably 0.6 mass% or less. When the saturated water absorption rate is 1.0% by mass or less, the resin composition of the present invention is excellent in moisture resistance, and it is possible to suppress the warping of the laminate resulting from moisture absorption.

The MFR of the SMA resin (B) is preferably in the range of 1 to 10 g / 10 min. The lower limit value of the MFR is more preferably 1.2 g / 10 min or more, and further preferably 1.5 g / 10 min. The upper limit of the MFR is more preferably 7.0 g / 10 min or less, and further preferably 4.0 g / 10 min or less. When the MFR is in the range of 1 to 10 g / 10 min, the stability of hot melt molding is good.

The mass ratio (methacrylic resin (A) / SMA resin (B)) of the methacrylic resin (A) and the SMA resin (B) contained in the resin composition of the present invention suppresses occurrence of warpage at high temperature, But it is preferably in the range of 5/95 to 90/10 from the viewpoint of scratch resistance. The mass ratio is more preferably 10/90 or more, further preferably 15/85 or more, and particularly preferably 20/80 or more. Further, such a mass ratio is more preferably 85/15 or less, further preferably 80/20 or less, and particularly preferably 75/25 or less.

The methacrylic resin (A) and the SMA resin (B) may be mixed by, for example, a melt mixing method, a solution mixing method or the like. In the melt mixing method, a melt-kneading machine such as a single-screw or multiaxial 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, . In the solution mixing method, the methacrylic resin (A) and the SMA resin (B) are dissolved in an organic solvent such as toluene, tetrahydrofuran, or methyl ethyl ketone and mixed.

The resin composition of the present invention may contain a polymer other than the methacrylic resin (A) and the SMA resin (B) within a range that does not impair the effect of the present invention. Examples of such other polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene, ethylenic ionomers; Styrene 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; Nylon 6, nylon 66, and polyamide elastomers; Polyphenylene sulfide, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer , Polyacetal, and phenoxy resin; Thermosetting resins such as phenol resin, melamine resin, silicone resin and epoxy resin; Polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin; Acrylic rubber, silicone rubber; Styrene-based thermoplastic elastomers such as SEPS, SEBS and SIS; And olefin rubbers such as IR, EPR and EPDM. One kind of the other polymer may be used alone, or a plurality of kinds may be used in combination.

The content of the other polymer in the resin composition is preferably 10 mass% or less, more preferably 5 mass% or less, and further preferably 2 mass% or less.

The resin composition of the present invention may contain various additives as required. Examples of such additives include antioxidants, thermal degradation inhibitors, ultraviolet absorbers, light stabilizers, lubricants, release agents, polymer processing aids, antistatic agents, flame retardants, dyes and pigments, light diffusing agents, And the like. The content of these additives can be appropriately set within a range that does not impair the effect of the present invention. For example, the content of the antioxidant is 0.01 to 1 part by mass, the content of the ultraviolet absorber is, for example, 0.01 to 3 parts by mass of the light stabilizer, 0.01 to 3 parts by mass of the light stabilizer, 0.01 to 3 parts by mass of the lubricant, and 0.01 to 3 parts by mass of the dye and pigment.

The antioxidant is effective in preventing oxidative deterioration of the resin in the presence of oxygen. Examples thereof include phosphorus antioxidants, phenol antioxidants, sulfur antioxidants, amine antioxidants and the like. Among them, a phosphorus-based antioxidant and a phenol-based antioxidant are preferable from the viewpoint of an effect of preventing deterioration of optical characteristics due to coloring, and a combination of a phosphorus-based antioxidant and a phenol-based antioxidant is more preferable. When the phosphorus-based antioxidant and the phenol-based antioxidant are used in combination, it is preferable to use the phosphorus-based antioxidant / the phenol-based antioxidant in a mass ratio of 0.2: 1 to 2: 1, more preferably 0.5: 1 to 1: 1 desirable.

Examples of the phosphorus antioxidant include 2,2-methylenebis (4,6-dit butylphenyl) octylphosphite (Adekastab HP-10 manufactured by ADEKA Corporation), tris (2,4-di- Phenyl) phosphite ("IRGAFOS168" manufactured by BASF Japan KK), 3,9-bis (2,6-di-tert- 9-diphosphaspiro [5.5] undecane ("Adekastab PEP-36" manufactured by ADEKA Corporation) is preferable.

Examples of the phenol antioxidant include pentaerythrityl-tetrakis [3- (3,5-ditbutyl-4-hydroxyphenyl) propionate] (IRGANOX1010 manufactured by BASF Japan KK, octadecyl- - (3,5-ditert-butyl-4-hydroxyphenyl) propionate (IRGANOX1076 manufactured by BASF Japan KK).

As the thermal deterioration preventing agent, thermal degradation of the resin can be prevented by replenishing the polymer radical generated when the resin is exposed to a high temperature under substantially anaerobic conditions. Examples of the thermal deterioration preventing agent include 2-t-butyl-6- (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenylacrylate ("Sumilizer GM" Phenyl-acrylate ("Sumilizer GS" manufactured by Sumitomo Chemical Co., Ltd.) and the like, desirable.

The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. The ultraviolet absorber is a compound which is said to have a function of mainly converting light energy into thermal energy. Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, anilides oxalic acid, malonic acid esters and formamidines. Among them, an ultraviolet absorber having benzotriazoles, triazines, or a maximum value? _Max of a molar extinction coefficient at a wavelength of 380 to 450 nm of 1200 dm ³ ㏖ ^-1 cm ^-1 or less is preferable. These ultraviolet absorbers may be used alone or in combination of two or more.

Since benzotriazoles have a high effect of suppressing deterioration in optical properties such as coloration caused by ultraviolet ray irradiation (irradiation), they are preferable as the ultraviolet absorber for use in application of the resin composition of the present invention to optical applications. Examples of the benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (trade name: TINUVIN 329, manufactured by BASF Japan KK) Methyl-1-phenylethyl) phenol (trade name "TINUVIN234" manufactured by BASF Japan KK), 2,2'-methylenebis [6- -Benzotriazol-2-yl) -4-tert-octylphenol] ("Adekastab LA-31" manufactured by ADEKA CORPORATION).

In the case where a wavelength near 380 nm is desirably absorbed, a triazine ultraviolet absorber is preferably used. Examples of such ultraviolet absorbers include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (Adekastab LA-F70 ), And a hydroxyphenyltriazine based ultraviolet absorber ("TINUVIN477" or "TINUVIN460" manufactured by BASF Japan Co., Ltd.), which is a flexible substance.

The ultraviolet absorbing agent containing sulfur in the skeleton is preferable in the case of adapting the resin composition of the present invention to optical use because it can increase the refractive index of the resin composition in addition to ultraviolet ray absorbing ability. Examples of the ultraviolet absorber containing sulfur in the skeleton include 2- (5-octylthio-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol (Compound A) 2-yl) -6-tert-butyl-4-methylphenol (Compound B). As the triazines, 2,4-diphenyl-6- (2-hydroxy-4-methylthiophenyl) -1,3,5-triazine (Compound C), 2,4,6- 4-hexylthiophenyl) -1,3,5-triazine (Compound D).

The ultraviolet absorber containing sulfur in the skeleton may increase the refractive index of the resin composition, but may have absorption in a visible light region having a wavelength of 380 nm or more, which may cause the resin composition to be colored. Therefore, it is preferable to use it in combination with another ultraviolet absorber.

When the ultraviolet absorber is used in combination, the benzotriazoles [1] containing no sulfur in the skeleton, the triazoles [2] containing no sulfur in the skeleton [2] and the ultraviolet absorber For example, [1] and [2]; [1] and [3]; [2] and [3]: [1] and [2] and [3]; . ≪ / RTI > [4] may also be used in combination with an ultraviolet absorber which does not correspond to any of [1] to [3].

The light stabilizer is a compound which is said to have a function of capturing a radical mainly generated by light oxidation. Preferable examples of the light stabilizer include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton. For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate ("Adekastab LA-77Y" manufactured by ADEKA Corporation) and the like can be mentioned.

The lubricant is a compound which is said to have an effect of improving releasability and workability by preventing slippage of a polymer and a metal surface to prevent adhesion or sticking. Examples thereof include higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, fatty acid esters, and the like. Of these, aliphatic monohydric alcohols having 12 to 18 carbon atoms are preferable from the viewpoint of compatibility with the resin composition of the present invention. Examples thereof include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and the like.

The methacrylic resin (A) and / or the SMA resin (B) may be added when the other polymer and / or additive is contained in the resin composition of the present invention, ), Or may be added after mixing the methacrylic resin (A) and the SMA resin (B).

The glass transition temperature of the resin composition of the present invention is preferably in the range of 115 to 160 ° C. The lower limit of the glass transition temperature is more preferably 120 ° C or higher, more preferably 130 ° C or higher, and most preferably 140 ° C or higher. The upper limit of the glass transition temperature is more preferably 155 deg. C or lower, and further preferably 150 deg. C or lower. When the glass transition temperature is in the range of 115 to 160 占 폚, the occurrence of warpage at a high temperature of the molded article made of the resin composition of the present invention can be suppressed.

The saturated water absorption rate of the resin composition of the present invention in water at 23 캜 is preferably 1.9 mass% or less, more preferably 1.5 mass% or less, and further preferably 1.0 mass% or less. When the saturated water absorption rate is 1.9 mass% or less, the resin composition of the present invention is excellent in moisture resistance, and warpage of the laminate due to moisture absorption can be suppressed.

The MFR of the resin composition of the present invention is preferably in the range of 1 to 10 g / 10 min. The lower limit value of the MFR is more preferably 1.5 g / 10 min or more, and still more preferably 2.0 g / 10 min. The upper limit of the MFR is more preferably 7.0 g / 10 min or less, and further preferably 4.0 g / 10 min or less. When the MFR is in the range of 1 to 10 g / 10 min, the stability of hot melt molding is good.

Extrusion molding methods such as a co-extrusion molding method, a T-die laminate molding method, and an extrusion coating method; An injection molding method such as an insert injection molding method, a two-color injection molding method, a core bag injection molding method, a sandwich injection molding method, and an injection press molding method; Blow molding method; Calendar forming method; Press forming method; And various molding products can be obtained by hot melt molding by a slush molding method or the like. The resin composition of the present invention is suitable for the production of a molded article requiring high temperature or long-term residence condition because the gel is not well formed even after long-term melt molding at a high temperature. The resin composition of the present invention is preferable for the production of thin and wide shaped articles such as sheets, films, plates and the like.

[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. Other materials used in the laminate of the present invention are not particularly limited. For example, organic materials such as resins; Metal materials, metal oxides, and the like.

The laminate related to one embodiment of the present invention has at least one layer made of the resin composition [C1] and at least one layer made of the resin composition [C2] which is another 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 resin, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, But are not limited to, an alcohol copolymer, a polyacetal, a polyvinylidene fluoride, a polyurethane, a modified polyphenylene ether, a polyphenylene sulfide, a silicone modified resin, a polyether ether ketone, a polysulfone, a polyphenylene oxide, Phenoxy resins; Thermosetting resins such as phenol resin, melamine resin, silicone resin and epoxy resin; Energy ray-curable resin, and the like. The resin of the resin composition [C2] may be used alone or in combination of two or more. Among these, a thermoplastic resin is preferable, and a polycarbonate is more preferable.

When polycarbonate is employed as the resin, the amount of the polycarbonate contained in the resin composition [C2] is preferably 90 mass% or more, more preferably 95 mass% or more, and further preferably 98 mass% or more. The weight average molecular weight of such polycarbonate is preferably 20,000 to 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 manufactured. The polycarbonate has a Mw / Mn of preferably 1.7 to 2.6, more preferably 1.7 to 2.3, and still more preferably 1.7 to 2.0.

The polycarbonate may be a commercially available product, for example, "Kaliba (registered trademark)" manufactured by Sumikastar Theory Polycarbonate Co., Ltd., "Yuplon / Novarex (registered trademark)" manufactured by Mitsubishi Engineering Plastics Corporation, "Tafron (registered trademark)" manufactured by JEOL Ltd., "Panlite (registered trademark)" manufactured by Dejima Chemical Co., Ltd., and the like can be preferably used.

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. It is preferable that the resin composition [C2] has a glass transition temperature that is the same as the glass transition temperature of the resin composition [C1]. Specifically, the absolute value |? Tg | of the difference 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 lower, more preferably 20 ° C or lower. If? Tg | is 30 占 폚 or less, the effect of suppressing the occurrence of warpage under high temperature and high humidity of the laminated body is further enhanced.

The resin composition [C2] used in the present invention is preferably a thermoplastic resin composition (T) having a saturated water absorption rate at 23 ° C in water of 0.1 to 1.0 mass%. The thermoplastic resin composition (T) is preferably a resin composition containing a polycarbonate. The resin composition [C2] is preferably such that its saturation absorption rate is the same as the saturation absorption rate of the resin composition [C1]. Specifically, the absolute value of the difference between the saturation absorption rate of the resin composition [C2] and the saturation absorption rate of the resin composition [C1] is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. When the difference in saturated water absorption between the both resins is 1.5 mass% or less, the effect of suppressing the occurrence of warpage under high temperature and high humidity of the laminated body is further enhanced.

The resin composition [C2] used in the present invention is preferably a thermoplastic resin composition (T) having a melt volume rate (hereinafter referred to as "MVR") of 1 to 30 cm 3/10 min. The MVR is more preferably in the range of 3 to 20 cm 3/10 min, and still more preferably in the range of 6 to 10 cm 3/10 min.

In the present specification, the MVR is measured using a melt indexer under conditions of a temperature of 300 DEG C and a load of 1.2 kg.

The resin composition [C2] used in the present invention may contain known additives in order to improve the heat decomposition resistance, heat discoloration resistance, light resistance and the like. Examples of additives include antioxidants, heat deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, release agents, polymer processing aids, antistatic agents, flame retardants, salt pigments, light diffusers, organic pigments, polish remover, impact resistance modifiers, .

The laminate related to another embodiment of the present invention is a laminate comprising at least one layer [L1] comprising a resin composition [C1], at least one layer [L2] comprising a resin composition [C2] L3]. The functionality-imparting layer [L3] is not particularly limited. For example, an abrasion-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 and an impact strength- The functionality-imparting layer [L3] can be formed by a known method. For example, the hard coat layer can be obtained by applying a resin solution for hard coat, followed by drying and curing. The antireflection layer can be obtained by laminating a low refractive index film and a high refractive index film by vapor deposition or the like. Among the function imparting layer [L3], for example, the scratch-resistant layer, the hard coat layer, the antistatic layer, the antifouling layer, the friction reducing layer, the antiglare layer, the antireflection layer and the like are generally formed on the outermost side of the laminate. The functional imparting layer [L3] may be formed of only one kind, or plural kinds of functional imparting layers [L3] may be formed. The laminate of the present invention preferably has an abrasion-resistant layer on at least one surface from the viewpoint of enhancing scratch resistance.

The layer structure in the laminate of the present invention is not particularly limited. As a lamination sequence of the laminate of the present invention, the layer composed of the resin composition [C1] is referred to as a layer [L1], the layer composed of the resin composition [C2] is referred to as a layer [L2], the function imparting layer [L3] For example, a layer [L1] / [L2], a layer [L1] / a layer [L2] / a layer [L1], a layer / a layer / [L1] layer / [L2] layer / [L1] layer / [L2] layer / [L1] layer, [L1] layer / [L2] layer / [L3] [L1] layer, [L1] layer, [L2] layer, [L3] layer, [L1] ] / [L2] / [L3] / [L2] / [L1] For example, when the [L3] layer is a hard coat layer, the [L3] layer / [L1] / [L2] layer, [L3] layer / [L1] layer / [L2] [L3] layer / [L1] layer / [L2] layer / [L1] layer / [L3] layer is preferable.

The present invention is useful in a laminate having a shape such as a sheet, a thin plate, a film, or the like. When the laminate related to the present invention is used as a protective cover, it is preferable to arrange the resin composition [C1] layer so as to be located on the outer side of the resin composition [C2] layer when viewed from the protected surface (protected surface). For example, a laminate composed of the layer structure of the [L1] layer / [L2] layer is arranged in the order of [L1] layer / [L2] / [L1] layer / protective layer is preferably arranged in the order of [L1] layer / [L2] layer / [L1] layer / protected surface.

The total thickness of the laminate related to the present invention can be set depending on the application, but is preferably 0.2 to 2 mm, and more preferably 0.3 to 1.5 mm. If it is too thin, the rigidity tends to become insufficient. If it is excessively large, the weight of the liquid crystal display device tends to be hindered.

The thickness of the layer made of the resin composition [C1] in the laminate related to the present invention is preferably in the range of 0.02 to 0.5 mm. The lower limit value of the thickness of this layer is more preferably 0.03 mm or more, and more preferably 0.05 mm or more. Further, the upper limit value of the thickness of such a layer is more preferably 0.3 mm or less, and further preferably 0.1 mm or less. When the thickness is less than 0.01 mm, scratch resistance and weather resistance may be insufficient. If it exceeds 0.5 mm, the impact resistance may be insufficient.

From the viewpoint of suppressing the occurrence of warping at a high temperature, it is preferable that the laminate related to the present invention is laminated in the order of symmetry in the thickness direction, and the thickness of each layer is more preferably symmetrical.

The laminate related to the present invention can be produced by a multilayer molding method such as multilayer extrusion molding, multilayer blow molding, multilayer press molding, multicolor injection molding, insert injection molding or the like without particular limitation by the production method thereof have. Among these multilayer molding methods, multilayer extrusion molding of the resin composition [C1] and the resin composition [C2] is preferable from the viewpoint of productivity.

The method of multilayer extrusion molding is not particularly limited, and a known multilayer extrusion molding method used for producing a multilayer laminate of a thermoplastic resin is adopted, and for example, a device having a flat T die and a polished surface- . In the T-die method, the feed block method in which the resin composition [C1] and the resin composition [C2] in the molten state are laminated before the T die inlet, or the resin composition [C1] and the resin composition [C2] A multi-manifold system in which a plurality of stacked substrates are stacked. From the viewpoint of enhancing the smoothness of the interface between the respective layers constituting the laminate, the multi-manifold method is preferable.

The resin composition [C1] and the resin composition [C2] are preferably subjected to melt filtration by a filter before multilayer molding. By the multilayer molding using each resin composition melt-filtered, a laminated sheet having few defects derived from foreign matters, gel, or the like can be obtained. The filter used for the melt filtration is not particularly limited. The filter is suitably selected from among those known from the viewpoints of operating temperature, viscosity, required filtration accuracy, and the like. Specific examples of the filter include a nonwoven fabric made of polypropylene, cotton, polyester, viscose rayon, glass fiber or the like; Phenolic resin impregnated cellulose film; Metal fiber nonwoven sintered film; Metal powder sintered film; Wire mesh; Or a combination thereof. Among them, it is preferable to laminate a plurality of metal fiber nonwoven fabric sintered films in view of heat resistance, durability and pressure resistance.

The filtration accuracy of the filter is not particularly limited, but is preferably 30 占 퐉 or less, more preferably 10 占 퐉 or less, and further preferably 5 占 퐉 or less.

According to the resin composition of the present invention, it has excellent transparency, surface hardness and heat resistance. Therefore, the molded article and the laminate obtained by melt-molding the resin composition according to the present invention can be preferably used for an optical member and the like because they have good appearance, excellent scratch resistance, and small dimensional change.

Examples of the use of the molded article, molded article and laminated body according to the present invention include standard parts such as advertising towers, stand signboards, protruding signboards, pointed signboards, and rooftop signboards; Display parts such as showcase, partition plate, and store display; Fluorescent lamp covers, mood lighting covers, lamp shades, lighting fixtures, light walls, chandeliers and other lighting components; Interior parts such as pendants and mirrors; Architectural parts such as doors, domes, safety windowpanes, partitions, stair planks, balcony boards, and roofs of leisure buildings; Related parts of aircraft such as aircraft windshields, pilot visors, motorcycles, motor boat windshields, bus shields, automotive side visors, rear visors, head wings and headlight covers; Electronic device parts such as nameplates for acoustic images, stereo covers, television protective masks, and vending machine display covers; Medical device parts such as incubator, rheggen parts; Machine-related parts such as machine covers, instrument covers, experimental equipment, rulers, letter glasses, and observation windows; Optical related parts such as a liquid crystal protective plate, a light guide plate, a light guide film, a Fresnel lens, a lenticular lens, a front plate of various displays, and a diffusion plate; Traffic-related parts such as road signs, guide plates, curved mirrors, soundproof walls; A film member such as an automobile interior surface material, a surface material of a cellular phone, a transparent conductive film, a light guiding film, a polarizer protective film, and a marking film; A member for household appliances such as a lid of a washing machine, a control panel, and a lid panel of a heat-cooker; Other greenhouses, large water tanks, box tanks, watch panels, stubs, sanitary ware, desk mats, organic parts, toys, masks for face protection during welding and the like.

EXAMPLES The present invention will be described in more detail with reference to the following examples and comparative examples. However, the present invention is not limited to these examples.

[Resin Composition] The physical properties of the resin compositions obtained in Examples 1a to 3a and Comparative Examples 1a to 6a were measured by the following methods.

<Total light transmittance>

The resin composition according to the present invention was injection-molded under the conditions of a cylinder temperature of 280 占 폚, a mold temperature of 75 占 폚 and a molding cycle of 1 minute using an injection molding machine (SE-180DU-HP manufactured by Sumitomo Heavy Industries Co., Ltd.) Mm and a side of 50 mm square were obtained. Each test piece was measured using a spectral color difference meter SE5000 manufactured by Nippon Seimei Kogyo Co., Ltd. according to the method of JIS-K7361-1.

<Hayes>

A test piece comprising the resin composition according to the present invention was obtained by the same method as above. Each test piece was measured using a spectral color difference meter SE5000 manufactured by Nippon Seimei Kogyo Co., Ltd. according to the method of JIS-K7361.

<Rockwell hardness>

A test piece comprising the resin composition according to the present invention was obtained by the same method as above. Each test piece was measured on an M scale in accordance with the method of JIS-K7202-2 using a Rockwell hardness tester manufactured by Toyobo Co., Ltd., DXT-FA.

&Lt; Glass transition temperature (Tg) >

In accordance with JIS K7121, the resin composition according to the present invention was heated from room temperature to 250 占 폚 at 20 占 폚 / min, held for 5 minutes, cooled to -100 占 폚 at 10 占 폚 / min, (DSC) analysis was carried out at a temperature condition in which the temperature was raised to 10 / min. The midpoint glass transition temperature determined from the DSC curve measured at the time of the second temperature rise was adopted as the glass transition temperature in the present invention. As a measuring apparatus, Q-20 manufactured by TA Instruments Inc. was used.

<Saturation Absorption Rate>

A test piece comprising the resin composition according to the present invention was obtained by the same method as above. Under the conditions of a temperature of 80 캜 and a pressure of 5 mmHg, the test piece was vacuum-dried for 24 hours. Then, the test piece was cooled in a desiccator. The test piece was taken out from the desiccator and the mass (initial mass) was measured immediately.

Subsequently, the test piece was immersed in distilled water at 23 占 폚. The test piece was taken out of the water, and the water adhering to the surface was wiped off to measure the mass. 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 no mass change occurred. The saturation absorption rate was calculated from the mass (absorbed mass) when the mass change was eliminated and the initial mass by the following equation.

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

<Chemical resistance>

A test piece comprising the resin composition according to the present invention was obtained by the same method as above. 0.05 g of the ultraviolet screening agent shown in Table 1 was uniformly applied on the surface of the test piece, and then two aluminum pieces (75 mm x 150 mm x 1 mm) and weights (500 g) And allowed to stand under the temperature shown in Table 1 for 1 hour. Thereafter, the weight, the aluminum plate, and the test cloth were removed and the surface of the test piece was washed with a nonwoven wiper (cotton cigarette) impregnated with a neutral detergent. After naturally drying, the surface of the test piece was visually observed and evaluated according to the following criteria.

○: No change in appearance

△: There is no whisker mark attached, but a little whitish

X: There is an attached whitening mark, and remarkably white whitening

<Examples of various materials>

The following materials were used for the methacrylic resin (A) and the vinyl copolymer (B) containing the resin composition according to the present invention.

Methacrylic resin (A1): Parapet manufactured by Kuraray Co., Ltd.

(Mw = 82,000, MMA copolymerization ratio = 100%, MA copolymerization ratio = 0%, rr ratio = 52%)

Methacrylic resin (A2): Parapet manufactured by Kuraray Co., Ltd.

(Mw = 120,000, MMA copolymerization ratio = 93.6%, MA copolymerization ratio = 6.4%, rr ratio = 48%)

Methacrylic resin (A3): Parapet manufactured by Kuraray Co., Ltd.

(Mw = 79,000, MMA copolymerization ratio = 88.7%, MA copolymerization ratio = 11.3%, rr ratio = 45%)

Vinyl copolymer (B): Regispie manufactured by Denki Kagaku Kogyo Co.,

(Mw = 80,000, styrene / maleic anhydride / MMA = 56% / 18% / 26%)

&Lt; Example 1a >

70 parts by mass of the methacrylic resin (A1) and 30 parts by mass of the vinyl copolymer (B) were melted and kneaded at a cylinder temperature of 230 占 폚 using a biaxial kneader. Thereafter, the molten resin was extruded to obtain a pellet-shaped resin composition [1]. Table 2 shows the composition and physical properties of the resin composition [1].

&Lt; Example 2a >

The resin composition [2] was obtained in the same manner as in Example 1a except that the composition ratio of the resin composition was 50 parts by mass of the methacrylic resin (A1) and 50 parts by mass of the vinyl copolymer (B). Table 2 shows the composition and physical properties of the resin composition [2].

&Lt; Example 3a >

The resin composition [3] was obtained in the same manner as in Example 1a except that the composition ratio of the methacrylic resin (A1) and the vinyl-based copolymer (B) was changed to 30 parts by mass and 70 parts by mass, respectively. Table 2 shows the composition and physical properties of the resin composition [3].

&Lt; Comparative Example 1a >

A resin composition [4] was obtained in the same manner as in Example 1a except that methacrylic resin (A2) was used instead of methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [4].

&Lt; Comparative Example 2a >

A resin composition [5] was obtained in the same manner as in Example 2a except that methacrylic resin (A2) was used instead of methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [5].

<Comparative Example 3a>

A resin composition [6] was obtained in the same manner as in Example 3a except that the methacrylic resin (A2) was used instead of the methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [6].

&Lt; Comparative Example 4a >

A resin composition [7] was obtained in the same manner as in Example 1a except that the methacrylic resin (A3) was used instead of the methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [7].

&Lt; Comparative Example 5a >

A resin composition [8] was obtained in the same manner as in Example 2a except that the methacrylic resin (A3) was used instead of the methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [8].

&Lt; Comparative Example 6a >

A resin composition [9] was obtained in the same manner as in Example 3a except that methacrylic resin (A3) was used instead of methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [9].

As can be seen from the above results, the resin compositions (Examples 1a to 3a) related to the present invention are superior to the resin compositions (Comparative Examples 1a to 6a) It has excellent heat resistance, scratch resistance and moisture resistance because it has transition temperature, surface hardness and low saturation absorption rate. Also, the chemical resistance is excellent.

[Laminates] The properties of the laminates obtained in Examples 1b to 3b and Comparative Examples 1b to 6b were measured by the following methods.

<Transparency>

The total light transmittance of the laminate related to the present invention was measured using a spectral color difference meter SE5000 manufactured by Nippon Seimei Kogyo Co., Ltd. in accordance with the method of JIS-K7361-1. The haze of the laminate related to the present invention was measured using the same apparatus as the total light transmittance according to the method of JIS-K7361. ?, A total light transmittance of 90% or more or a haze of 0.3% or less;?, A total light transmittance of less than 90% and a haze of more than 0.3%;

<Pencil hardness>

And measured using a table movable pencil scratching tester (type P) (manufactured by TOYO KOGYO CO., LTD.). The surface of the layer of the resin composition of the laminate related to the present invention was pressed against the surface of the pencil at an angle of 45 degrees and a load of 750 g to confirm whether or not scratches were scratched. The pencil hardness of the pencil was increased in order, and the pencil hardness was determined as the pencil hardness of the one-step shim than the point at which the scratches were generated. A pencil hardness of not less than H was rated as &amp; cir &amp; F, &amp; cir &amp;

<Change in warpage>

A rectangular test piece having a short side of 65 mm and a long side of 110 mm was cut out from the laminate related to the present invention such that the direction perpendicular to the direction of extrusion flow was a short side and the direction parallel to the direction of extrusion flow was a long side. After standing for 4 hours in an environmental tester set at a temperature of 75 ° C and a relative humidity of 50%, the specimen was allowed to cool to 25 ° C, and the test specimen was warped to an acute angle. This is considered to be a bending caused by the influence of molding conditions. The test piece bent in an acute angle was placed on a table so that the end of the test piece was in contact with the table (that is, the test piece was in a mountain shape) and the maximum distance between the table and the test piece ) Was measured using a gap gauge. This value was defined as the initial amount of warpage.

Subsequently, the short side of the test piece bent in an acute angle was picked up and left for 72 hours in an environmental tester set at a temperature of 85 캜 and a relative humidity of 85%. The maximum distance between the platen and the test piece was measured in the same manner as above after the test piece was cured for 4 hours in an environmental tester set at 25 캜 and 50% relative humidity. The difference between this measured value and initial bending amount was defined as &quot; bending change amount &quot;. A value of not less than 0.5 and not more than 1.0 was rated as?, And a value of not less than 1.0 mm was evaluated as?.

<Chemical resistance>

The laminate was cut into a square of 50 mm on one side, and used as a test piece. 0.05 g of the ultraviolet screening agent shown in Table 1 was uniformly applied to the surface of the layer made of the resin composition of the test piece, and then two sheets of test cloths (single fibrils), an aluminum plate (75 mm x 150 mm x 1 mm) The weight (500 g) was placed and left under the temperature shown in Table 1 for 1 hour. Thereafter, the weight, the aluminum plate, and the test cloth were removed and the surface of the test piece was washed with a nonwoven wiper (cotton cigarette) impregnated with a neutral detergent. After naturally drying, the surface of the test piece was visually observed and evaluated according to the following criteria.

○: No change in appearance

△: There is no whisker mark attached, but a little whitish

X: There is an attached whitening mark, and remarkably white whitening

&Lt; Light resistance of polycarbonate layer >

Laminate Test piece and a resin composition having no polycarbonate layer [1] - [3] were irradiated with ultraviolet rays to measure a color difference (? E) according to JIS Z-8730. The test piece of the laminate was irradiated with ultraviolet rays beside the layers of the resin composition [1] to [3]. The value obtained by subtracting the color difference of the resin composition single-layer film from the color difference of the laminate having the polycarbonate layer was defined as the color difference of the polycarbonate layer.

Test Methods :

Tester: Manufactured by Iwasaki former article Super-UV tester SUV-F1

Colorimeter: Color analyzer C-2000 manufactured by Hitachi, Ltd.

Exposure time: 24 hours

&Lt; Example 1b >

Pellets of polycarbonate (&quot; SD Polycar (registered trademark) PCX &quot;, manufactured by Sumikastar Theory Polycarbonate Co., Ltd., hereinafter the same) were fed into 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 / Were continuously added. Pellets of the resin composition [1] were continuously introduced into a uniaxial extruder [II] 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.

Polycarbonate and the resin composition [1] were simultaneously extruded from the extruder [I] and the extruder [II] and passed through a Pleats type cylindrical filter (manufactured by Fuji Filter Industry Co., Ltd.) And then introduced into a juncion block. Then, the polycarbonate and the resin composition [1] were co-extruded at a temperature of 245 DEG C using a multi-manifold die (Nordson Co., Ltd.) having a resin outlet width of 1600 mm and a lip interval of 2.0 mm Respectively. This sheet was subjected to bank formation between rolls 1 and 2 of four transverse rolls and cooled while transferring the specular surface with four rolls to obtain a layer composed of the resin composition [1] having a thickness of 80 탆 and a layer of polycarbonate having a thickness of 920 탆 Thereby obtaining a laminate having a total thickness of 1000 mu m.

&Lt; Example 2b >

A layer made of the resin composition [2] having a thickness of 80 占 퐉 and a layer made of polycarbonate having a thickness of 920 占 퐉 was formed in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [2] Was obtained.

&Lt; Example 3b >

A laminate of a resin layer [3] having a thickness of 80 [mu] m and a layer made of polycarbonate having a thickness of 920 [mu] m was formed in the same manner as in Example 1b except that the resin composition [1] Was obtained.

<Example 1c>

A laminate was obtained in the same manner as in Example 1b except that 1.0 part by mass of a benzotriazole-based ultraviolet absorber (LA31RG; manufactured by Adeka) was added per 100 parts by mass of the resin composition [1]. The ΔE of the polycarbonate layer by ultraviolet irradiation was 15 or more in Example 1b and 0.5 or less in Example 1c.

&Lt; Example 2c >

A laminate was obtained in the same manner as in Example 1c except that the resin composition [2] was used. The? E of the polycarbonate layer was 15 or more in Example 2b and 0.5 or less in Example 2c.

<Example 3c>

A laminate was obtained in the same manner as in Example 1c except that the resin composition was changed to the resin composition [3]. The ΔE of the polycarbonate layer was 15 or more in Example 3b and 0.5 or less in Example 3c.

<Comparative Example 1b>

A layer made of a resin composition [4] having a thickness of 80 占 퐉 and a layer made of polycarbonate having a thickness of 920 占 퐉 was formed in the same manner as in Example 1b except that the resin composition [1] was changed to the resin composition [4] Was obtained.

<Comparative Example 2b>

A total thickness of 1000 占 퐉 consisting of a layer made of the resin composition [5] having a thickness of 80 占 퐉 and a layer made of polycarbonate having a thickness of 920 占 퐉 was prepared in the same manner as in Example 1b except that the resin composition [1] Was obtained.

&Lt; Comparative Example 3b >

A total thickness of 1000 占 퐉 consisting of a layer made of the resin composition [6] having a thickness of 80 占 퐉 and a layer made of polycarbonate having a thickness of 920 占 퐉 was prepared in the same manner as in Example 1b except that the resin composition [1] Was obtained.

&Lt; Comparative Example 4b &

A total thickness of 1000 占 퐉 consisting of a layer made of the resin composition [7] having a thickness of 80 占 퐉 and a layer made of polycarbonate having a thickness of 920 占 퐉 was prepared in the same manner as in Example 1b except that the resin composition [1] Was obtained.

<Comparative Example 5b>

A total thickness of 1000 占 퐉 consisting of a layer made of the resin composition [8] having a thickness of 80 占 퐉 and a layer made of polycarbonate having a thickness of 920 占 퐉 was prepared in the same manner as in Example 1b except that the resin composition [1] Was obtained.

&Lt; Comparative Example 6b &

A total thickness of 1000 占 퐉 consisting of a layer made of the resin composition [9] having a thickness of 80 占 퐉 and a layer made of polycarbonate having a thickness of 920 占 퐉 was prepared in the same manner as in Example 1b except that the resin composition [1] Was obtained.

Table 3 shows the evaluation results of Examples 1b to 3b and Comparative Examples 1b to 6b.

As can be seen from the above results, the laminate related to the present invention (Examples 1b to 3b) has high pencil hardness and chemical resistance while maintaining transparency. It can also be seen that the laminate related to the present invention has less warpage even if it is left under high temperature and high humidity.

Claims (17)

(Meth) acrylate having a structural unit derived from an aromatic vinyl compound (b1) represented by at least the following general formula (1) and a structural unit derived from an aromatic vinyl compound And 10 to 95% by mass of a vinyl copolymer (B) comprising a structural unit derived from a cyclic acid anhydride (b2) represented by the following general formula (2).
[Chemical Formula 1]

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

(Wherein R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group) The method according to claim 1,
Wherein the methacrylic resin (A) contains 99.5 mass% or more of a structural unit derived from methyl methacrylate. 3. The method according to claim 1 or 2,
, Wherein the methacrylic resin (A) has a syndiotacticity (rr) in a triplet state of not less than 50%. 4. The method according to any one of claims 1 to 3,
A resin composition comprising 30 to 60% by mass of a methacrylic resin (A) and 40 to 70% by mass of a vinyl-based copolymer (B). 5. The method according to any one of claims 1 to 4,
The vinyl-based copolymer (B) contains 50 to 84% by mass of a structural unit derived from an aromatic vinyl compound (b1), 15 to 49% by mass of a structural unit derived from the cyclic acid anhydride (b2) And 1 to 35 mass% of a structural unit derived from the methacrylic acid ester (b3). 6. The method of claim 5,
And the methacrylic acid ester (b3) is methyl methacrylate. 7. The method according to any one of claims 1 to 6,
Wherein the glass transition temperature is from 115 to 160 占 폚. 8. The method according to any one of claims 1 to 7,
A resin composition containing an ultraviolet absorber. 9. The method of claim 8,
Wherein the ultraviolet absorber has a benzotriazole skeleton. 9. The method of claim 8,
Wherein the ultraviolet absorber has a triazine skeleton. 11. The method according to any one of claims 8 to 10,
Wherein the ultraviolet absorber contains sulfur in its skeleton. The method according to any one of claims 8 to 11,
A resin composition containing two or more ultraviolet absorbers. A molded article comprising the resin composition according to any one of claims 1 to 12. A resin composition comprising a layer comprising the resin composition according to any one of claims 1 to 12,
And a layer comprising a thermoplastic resin composition (T) having a glass transition temperature in the range of 130 to 160 占 폚. 15. The method of claim 14,
Wherein the thermoplastic resin composition (T) is a resin composition containing polycarbonate. 16. The method according to claim 14 or 15,
Wherein the absolute value of the difference between the thermoplastic resin composition (T) and the Tg of the resin composition is 30 占 폚 or less. 17. The method according to any one of claims 14 to 16,
Wherein at least one surface of the laminate further comprises an abrasion-resistant layer.