JPWO2017030147A1 - Resin composition, molded article and laminate - Google Patents

Abstract

A resin composition having high transparency, high surface hardness, chemical resistance, and high glass transition temperature is provided. Moreover, the molded article and laminated body using the said resin composition are provided. SOLUTION: It is derived from 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 at least an aromatic vinyl compound (b1) represented by the following general formula (1). A resin composition comprising 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). (In the formula, R1 and R2 each independently represent a hydrogen atom or an alkyl group.) (In the formula, R3 and R4 each independently represent a hydrogen atom or an alkyl group.) [Selection] None

Description

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

A methacrylic resin excellent in transparency, scratch resistance, weather resistance and the like is useful as a material for a molded product used for an optical member, a lighting member, a signboard member, a decorative member, and the like. However, since a methacrylic resin has a low glass transition temperature of about 110 ° C., a molded body made of the resin has a problem that it is easily deformed by heat.
As a method for increasing the glass transition temperature of a methacrylic resin, a method of polymer blending a methacrylic resin with a copolymer resin (SMA resin) composed of styrene and maleic anhydride is known. For example, Non-Patent Document 1 discusses polymer blends of various SMA resins having different copolymerization ratios of methacrylic resin and maleic anhydride, and SMA resin containing 8 to 33% by mass of maleic anhydride is methacrylic. It has been reported that it is compatible with a resin and has a higher glass transition temperature than a methacrylic resin. Patent Document 1 reports that a polymer blend of a copolymer of styrene, maleic anhydride, and methyl methacrylate and a methacrylic resin has a high glass transition temperature and low water absorption. Furthermore, Patent Document 2 discloses a laminate including a layer made of a resin composition containing a methacrylic resin and an SMA resin and a layer made of a polycarbonate.

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

C. R. BRANNOCK, 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 these methods has a problem that the surface hardness and chemical resistance decrease due to the influence of the SMA resin. By reducing the composition ratio of the SMA resin, it is possible to suppress a decrease in surface hardness and chemical resistance, but the glass transition temperature of the resulting resin composition becomes insufficient.

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

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

（式中のＲ^１およびＲ^２は、それぞれ独立して水素原子またはアルキル基を表す。）

（式中のＲ^３およびＲ^４は、それぞれ独立して水素原子またはアルキル基を表す。）
［２］ 前記メタクリル樹脂（Ａ）が、メタクリル酸メチルに由来する構造単位を９９．５質量％以上含むことを特徴とする［１］に記載の樹脂組成物。
［３］ 前記メタクリル樹脂（Ａ）が、三連子表示のシンジオタクティシティ（ｒｒ）が５０％以上であることを特徴とする［１］または［２］に記載の樹脂組成物。
［４］ メタクリル樹脂（Ａ）３０〜６０質量％と、ビニル系共重合体（Ｂ）４０〜７０質量％とを含有する［１］〜［３］のいずれかに記載の樹脂組成物。
［５］ ビニル系共重合体（Ｂ）は、芳香族ビニル化合物（ｂ１）に由来する構造単位を５０〜８４質量％含有し、環状酸無水物（ｂ２）に由来する構造単位を１５〜４９質量％含有し、メタクリル酸エステル（ｂ３）に由来する構造単位を１〜３５質量％含有する［１］〜［４］のいずれかに記載の樹脂組成物。
［６］ メタクリル酸エステル（ｂ３）がメタクリル酸メチルである［５］に記載の樹脂組成物。
［７］ ガラス転移温度が、１１５〜１６０℃である［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ 紫外線吸収剤を含有する［１］〜［７］のいずれか１項に記載の樹脂組成物。
［９］ 前記紫外線吸収剤が、ベンゾトリアゾール骨格を有することを特徴とする［８］に記載の樹脂組成物。
［１０］ 前記紫外線吸収剤が、トリアジン骨格を有することを特徴とする［９］に記載の樹脂組成物。
［１１］ 前記紫外線吸収剤が、その骨格内に硫黄を含有することを特徴とする［８］〜［１０］のいずれかに記載の樹脂組成物。
［１２］ 2種類以上の紫外線吸収剤を含有する［８］〜［１１］のいずれかに記載の樹脂組成物。
［１３］ ［１］〜［１２］のいずれかに記載の樹脂組成物を具備する成形品。
［１４］ ［１］〜［１２］のいずれかに記載の樹脂組成物からなる層と、ガラス転移温度が１３０〜１６０℃の範囲にある熱可塑性樹脂組成物（Ｔ）からなる層とを具備する積層体。
［１５］ 熱可塑性樹脂組成物（Ｔ）が、ポリカーボネートを含有する樹脂組成物である［１４］に記載の積層体。
［１６］ 熱可塑性樹脂組成物（Ｔ）と前記樹脂組成物とのＴｇの差の絶対値３０℃以下である［１４］又は［１５］に記載の積層体。
［１７］ 少なくとも一方の表面に、さらに耐擦傷性層を備える［１４］〜［１６］のいずれかに記載の積層体。[1] A structure derived from 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 at least an aromatic vinyl compound (b1) represented by the following general formula (1) A resin composition comprising 10 to 95% by mass of a vinyl copolymer (B) comprising a unit and a structural unit derived from a cyclic acid anhydride (b2) represented by the following general formula (2).

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

(In the formula, 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 as described in [1] or [2], wherein the methacrylic resin (A) has a triadic syndiotacticity (rr) of 50% or more.
[4] The resin composition according to any one of [1] to [3], comprising 30 to 60% by mass of methacrylic resin (A) and 40 to 70% by mass of vinyl copolymer (B).
[5] The vinyl copolymer (B) contains 50 to 84% by mass of a structural unit derived from the aromatic vinyl compound (b1), and 15 to 49 structural units derived from the cyclic acid anhydride (b2). The resin composition according to any one of [1] to [4], which is contained by mass and contains 1 to 35 mass% of a structural unit derived from a methacrylic acid ester (b3).
[6] The resin composition according to [5], wherein the methacrylate (b3) is methyl methacrylate.
[7] The resin composition according to any one of [1] to [6], which has a glass transition temperature of 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 as described in 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 kinds of ultraviolet absorbers.
[13] A molded article comprising the resin composition according to any one of [1] to [12].
[14] A layer made of the resin composition according to any one of [1] to [12] and a layer made of the thermoplastic resin composition (T) having a glass transition temperature in the range of 130 to 160 ° C. Laminated body.
[15] The laminate according to [14], wherein the thermoplastic resin composition (T) is a resin composition containing polycarbonate.
[16] The laminate according to [14] or [15], which has an absolute value of 30 ° C. or less of a difference in Tg between the thermoplastic resin composition (T) and the resin composition.
[17] The laminate according to any one of [14] to [16], further comprising a scratch-resistant layer on at least one surface.

  The resin composition according to the present invention is a resin composition containing a methacrylic resin and an SMA resin, and has high surface hardness, chemical resistance, and high glass transition temperature without reducing the high transparency characteristic of the methacrylic resin. The resin composition and a molded product and a laminate including the resin composition can be provided.

  Hereinafter, an example of an embodiment to which the present invention is applied will be described. In addition, the numerical value specified by this specification shows the value obtained when it measures by the method described in the Example mentioned later. For example, the weight average molecular weight Mw is a standard polystyrene conversion value measured by GPC (gel permeation chromatography), and shows a value obtained when measured by the method described in Examples described later. In addition, the numerical values “A to B” specified in the present specification indicate a range that is larger than the numerical value A and the numerical value A and satisfies the value smaller than the numerical value B and the numerical value B.

（式中のＲ^１およびＲ^２は、それぞれ独立して水素原子またはアルキル基を表す。）

（式中のＲ^３およびＲ^４は、それぞれ独立して水素原子またはアルキル基を表す。）[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 represented by the following general formula (2) It contains a vinyl copolymer (B) containing a structural unit derived from (b2) (hereinafter referred to as “SMA resin (B)”).

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

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

  Content of the methacryl resin (A) in the resin composition of this invention is the range of 5-90 mass%. The content of the methacrylic resin (A) in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and 30% by mass. The above is most preferable. In addition, 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, and further preferably 75% by mass or less, Most preferably, it is at most mass%. The layer composed of the resin composition of the present invention has excellent scratch resistance when the content of the methacrylic resin (A) in the resin composition is 5% by mass or more, and is 90% by mass or less. When laminated with other layers, the occurrence of warpage under high temperature and high humidity can be suppressed.

  The methacrylic resin (A) is 99% by mass or more, preferably 99.5% by mass or more, more preferably a structural unit derived from methyl methacrylate (hereinafter referred to as “MMA”) among all monomer units. Contains 100% by 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 improved. The content of the structural unit derived from MMA of the methacrylic resin (A) is obtained by subjecting the resin purified by reprecipitation of the methacrylic resin (A) in methanol to pyrolysis and volatile components using pyrolysis gas chromatography. Can be calculated from the ratio of the peak areas of the obtained MMA and the copolymerization component (mainly methyl acrylate).

  The methacrylic resin (A) contained in the resin composition of the present invention can contain a structural unit derived from a monomer other than MMA at 1% by mass or less, among all monomer units. The structural unit is preferably not included.

Examples of the monomer include structural units derived from methacrylic acid esters other than MMA. Examples of the methacrylic acid ester include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, methacrylic acid. Methacrylic acid alkyl esters such as 2-ethylhexyl acid, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, tricyclomethacrylate [5. 2.1.0 ^2,6] cycloalkyl methacrylate esters such as deca-8-yl; methacrylic acid aryl esters such as phenyl methacrylate; meta Methacrylic acid aralkyl esters such as acrylic acid benzyl; and the like. From the viewpoint of availability, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate are preferred. The content of structural units derived from methacrylic esters other than MMA in the methacrylic resin (A) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and derived from methacrylic esters other than MMA. Most preferably, no structural unit is included.

  In addition, examples of the monomer include structural units derived from monomers other than methacrylic acid esters. 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, and tert-acrylic acid. Butyl, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylic Cyclohexyl acid, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, acrylate acrylate And acrylic acid esters such as toluyl acrylate, benzyl acrylate, isobornyl acrylate, and 3-dimethylaminoethyl acrylate. From the viewpoint of availability, MA, ethyl acrylate, n-propyl acrylate, acrylic acid Acrylic esters such as isopropyl, n-butyl acrylate, isobutyl acrylate and tert-butyl acrylate are preferred, MA and ethyl acrylate are more preferred, and MA is most preferred. The total content of 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, and other single quantities other than methacrylic acid esters. Most preferably, it does not contain structural units derived from the body.

  The methacrylic resin (A) can be obtained by polymerizing MMA alone or other monomer which is an optional component. In the case of using a plurality of types of monomers in such polymerization, usually, such a plurality of types of monomers are mixed to prepare a monomer mixture and then subjected to polymerization. Although there is no particular limitation on the polymerization method, radical polymerization is preferably performed by a method such as a bulk polymerization method, a suspension polymerization method, a solution polymerization method, and an emulsion polymerization method from the viewpoint of productivity.

  In the methacrylic resin (A), the lower limit of the triplet-represented syndiotacticity (rr) is preferably 50% or more, more preferably 51% or more, and further preferably 52% or more. preferable. When the lower limit of the content of such a structure is 50% or more, the resin composition of the present invention has excellent heat resistance.

Here, the syndiotacticity (rr) in triplet display (hereinafter, simply referred to as “syndiotacticity (rr)”) is a chain of three consecutive structural units (triplet, triad). ) Is a ratio in which both chains (doublet, diad) are racemo (represented as rr). In the chain of molecular units (doublet, diad) in the polymer molecule, those having the same configuration are referred to as “meso”, and those opposite to each other are referred to as “racemo”, which are expressed as m and r, respectively.
The syndiotacticity (rr) (%) of the methacrylic resin (A) was determined by measuring a ¹ H-NMR spectrum at 30 ° C. in deuterated chloroform and setting tetramethylsilane (TMS) to 0 ppm from the spectrum. The area (X) of the region of 0.6 to 0.95 ppm and the area (Y) of the region of 0.6 to 1.35 ppm are measured and calculated by the formula: (X / Y) × 100 be able to.

  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 further preferably 80,000 to 200,000. . When the Mw is 40,000 or more, the resin composition of the present invention is excellent in mechanical strength, and when it is 500,000 or less, the compatibility with the SMA resin is good, and the resin of the present invention. Transparency of the molded body made of the composition can be increased.

  The glass transition temperature of the methacrylic resin (A) is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and further preferably 110 ° C. or higher. When the glass transition temperature is 100 ° C. or higher, the resin composition of the present invention has excellent heat resistance. In addition, the glass transition temperature in this specification is a temperature when it measures with the temperature increase rate of 10 degree-C / min using a differential scanning calorimeter, and is calculated by the midpoint method.

  The saturated water absorption in 23 ° C. water of the methacrylic resin (A) is preferably 2.5% by mass or less, more preferably 2.3% by mass or less, and 2.1% by mass or less. Further preferred. When the saturated water absorption is 2.5% by mass or less, the resin composition of the present invention has excellent moisture resistance and can suppress warping of the laminate due to moisture absorption. In addition, the saturated water absorption in this specification is the mass at the time when the molded product is immersed in 23 ° C. distilled water with respect to the mass of the molded product vacuum-dried for 3 days or more, the mass is measured over time, and the equilibrium is reached. It is a value measured as the rate of increase of.

  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 minutes. The lower limit value of MFR is more preferably 1.2 g / 10 minutes or more, and further preferably 1.5 g / 10 minutes. Further, the upper limit value of 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 minutes, the stability of heat-melt molding is good. In the present specification, the MFR of the resin composition of the present invention is a value measured using a melt indexer at a temperature of 230 ° C. and a load of 3.8 kg.

  Content of the SMA resin (B) in the resin composition of this invention is the range of 10-95 mass%. The content of the SMA resin (B) in the resin composition is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and 40% by mass or more. Most preferably. Further, the content of the SMA resin (B) in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and 70% by mass. % Is most preferred. When the laminate of the present invention is laminated with another layer because the content of the SMA resin (B) in the resin composition is 10% by mass or more, the occurrence of warpage under high temperature and high humidity can be suppressed, It is excellent in abrasion resistance because it is 95% by mass or less.

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

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

R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group or a t-butyl group. R ² , R ³ and R ⁴ are preferably a hydrogen atom, a methyl group and 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 60% by mass or more. More preferably. Further, 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 80% by mass or less. More preferably. When the content is in the range of 50 to 84% by 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 aromatic vinyl compound (b1) in the SMA resin (B) is used. The content of the structural unit derived from) is preferably in the range of 50 to 85% by mass.

  Examples of the aromatic vinyl compound (b1) include styrene; alkyl substituted styrenes such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene; α-methylstyrene , Α-alkyl-substituted styrene such as 4-methyl-α-methylstyrene; and styrene is preferable from the viewpoint of availability. These aromatic vinyl compounds (b1) may be used alone or in combination of two or more.

  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, more preferably 18% by mass or more, and 20% by mass or more. More preferably. 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, and 40% by mass or less. More preferably. When the content is in the range of 15 to 49% by mass, the resin composition of the present invention is excellent in heat resistance and transparency. However, when the SMA resin (B) consists of only two monomers, the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2), the cyclic acid anhydride (b2) in the SMA resin (B) The content of the structural unit derived from) is preferably in the range of 15 to 50% by mass.

  Examples of the cyclic acid anhydride (b2) include maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, and the like, and maleic anhydride is preferable from the viewpoint of availability. A cyclic acid anhydride (b2) may be used individually by 1 type, or may use multiple types together.

  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, and 5% by mass or more. Even more preferably, it is most preferably 10% by mass or more. Further, the content of the structural unit derived from the methacrylic acid ester (b3) in the SMA resin (B) is preferably 35% by mass or less, more preferably 30% by mass or less, and 26% by mass or less. More preferably it is. When the content is in the range of 1 to 35% by mass, the transparency and thermal stability are further improved.

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

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

  The SMA resin (B) is obtained by polymerizing at least the monomers of the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2). The monomer may be polymerized by adding the methacrylic acid ester (b3) and other optional monomers. In such polymerization, usually, the monomers to be used are mixed to prepare a monomer mixture and then subjected to polymerization. Although there is no restriction | limiting in particular in the polymerization method, From a viewpoint of productivity, it is preferable to radical-polymerize by methods, such as a block polymerization method and 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 resin composition of the present invention is excellent in mechanical strength, and when it is 300,000 or less, the compatibility with the methacrylic resin is improved, and the resin composition of the present invention. The transparency of a molded product made of a product can be increased.

  The glass transition temperature of the SMA resin (B) is preferably 115 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 125 ° C. or higher. When the glass transition temperature is 110 ° C. or higher, the resin composition of the present invention has excellent heat resistance, and the warpage of the laminate due to heat can be suppressed.

  The saturated water absorption of the SMA resin (B) in 23 ° C. water is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and 0.6% by mass or less. Further preferred. When the saturated water absorption is 1.0% by mass or less, the resin composition of the present invention has excellent moisture resistance and can suppress warping of the laminate due to moisture absorption.

  The MFR of the SMA resin (B) is preferably in the range of 1 to 10 g / 10 minutes. The lower limit value of MFR is more preferably 1.2 g / 10 minutes or more, and further preferably 1.5 g / 10 minutes. Further, the upper limit value of 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 minutes, the stability of heat-melt molding is good.

  The mass ratio of the methacrylic resin (A) and the SMA resin (B) contained in the resin composition of the present invention (methacrylic resin (A) / SMA resin (B)) suppresses the occurrence of warpage at high temperatures and is transparent From the viewpoint of scratch resistance, it 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 mixing the methacrylic resin (A) and the SMA resin (B), for example, a melt mixing method or a solution mixing method can be used. In the melt mixing method, for example, using a melt kneader such as a uniaxial or multiaxial kneader, an open roll, a Banbury mixer, a kneader, and the like, under an inert gas atmosphere such as nitrogen gas, argon gas, helium gas, etc. Perform melt-kneading. 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 composition of the present invention may contain a polymer other than the methacrylic resin (A) and the SMA resin (B) as long as the effects of the present invention are not impaired. Examples of such other polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1 and polynorbornene, ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, Styrenic resin such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-styrene copolymer; polyester such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, polyamide elastomer Polyamides such as polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polycarbonate Thermoplastic resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, phenoxy resin; thermosetting resins such as phenol resin, melamine resin, silicone resin, 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-based rubbers such as IR, EPR, and EPDM. Another polymer may be used individually by 1 type, or may use multiple types together.
The content of the other polymer in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.

  The resin composition of the present invention may contain various additives as necessary. Examples of such additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes / pigments, and light diffusing agents. , Matting agents, impact resistance modifiers, phosphors and the like. The content of these additives can be appropriately set within a range that does not impair the effects of the present invention. For example, the content of the antioxidant is 0.01 to 1 part by mass with respect to 100 parts by mass of the resin composition. The absorber content is 0.01 to 3 parts by mass, the light stabilizer content is 0.01 to 3 parts by mass, the lubricant content is 0.01 to 3 parts by mass, and the dye / pigment content is 0. It is preferable to set it as 0.01-3 mass parts.

  The antioxidant alone has an effect of preventing oxidative deterioration of the resin in the presence of oxygen. For example, phosphorus antioxidants, phenol antioxidants, sulfur antioxidants, amine antioxidants and the like can be mentioned. Among these, from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, a phosphorus-based antioxidant and a phenol-based antioxidant are preferable, and a combined use of a phosphorus-based antioxidant and a phenol-based antioxidant is more preferable. When a phosphorus antioxidant and a phenolic antioxidant are used in combination, it is preferable to use a phosphorus antioxidant / phenolic antioxidant at a mass ratio of 0.2 / 1 to 2/1. It is more preferable to use 5/1 to 1/1.

  As phosphorus antioxidants, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (“ADEKA STAB HP-10” manufactured by ADEKA Corporation), tris (2,4-di-t-butyl) Phenyl) phosphite (“IRGAFOS168” manufactured by BASF Japan Ltd.), 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9 -Diphosphaspiro [5.5] undecane (“ADEKA STAB PEP-36” manufactured by ADEKA Corporation) is preferable.

  As the phenolic antioxidant, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (“IRGANOX1010” manufactured by BASF Japan Ltd., octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate (“IRGANOX1076” manufactured by BASF Japan Ltd.) is preferred.

  The thermal degradation inhibitor can prevent thermal degradation of the resin by capturing polymer radicals generated when exposed to high temperatures under substantially oxygen-free conditions. As the thermal degradation inhibitor, 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (“Sumilyzer GM” manufactured by Sumitomo Chemical Co., Ltd.), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy-α-methylbenzyl) phenyl acrylate (“Sumilyzer GS” manufactured by Sumitomo Chemical Co., Ltd.) is preferred.

The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. The ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy. Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, and the like. Among these, benzotriazoles, triazines, or ultraviolet absorbers having a maximum molar extinction coefficient ε _{max at a} wavelength of 380 to 450 nm of 1200 dm ³ · mol ⁻¹ cm ⁻¹ or less are preferable. These ultraviolet absorbers may be used alone or in combination of two or more.

  Benzotriazoles are preferable as ultraviolet absorbers used when the resin composition of the present invention is applied to optical applications because it has a high effect of suppressing deterioration of optical properties such as coloring due to ultraviolet irradiation. Examples of benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (“trade name TINUVIN329” manufactured by BASF Japan Ltd.), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (“trade name TINUVIN234” manufactured by BASF Japan Ltd.), 2,2′-methylenebis [6- ( 2H-benzotriazol-2-yl) -4-tert-octylphenol] (“ADEKA STAB LA-31” manufactured by ADEKA Corporation) and the like are preferable.

  Further, when it is desired to efficiently absorb a wavelength around 380 nm, a triazine ultraviolet absorber is preferably used. As such an ultraviolet absorber, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (“ADEKA STAB LA-F70” manufactured by ADEKA Corporation) And hydroxyphenyltriazine-based ultraviolet absorbers (“TINUVIN477” and “TINUVIN460” manufactured by BASF Japan Ltd.) which are analogs thereof.

Since the ultraviolet absorber containing sulfur in the skeleton can increase the refractive index of the resin composition in addition to the ultraviolet absorbing ability, it is preferable when the resin composition of the present invention is applied to optical applications. 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) as benzotriazoles, 2- (5-dodecylthio-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol (Compound B). Further, as triazines, 2,4-diphenyl-6- (2-hydroxy-4-methylthiophenyl) -1,3,5-triazine (Compound C), 2,4,6- (2-hydroxy-4-to) Xylthiophenyl) -1,3,5-triazine (Compound D).
Although the ultraviolet absorber containing sulfur in the skeleton can increase the refractive index of the resin composition, it may have absorption in the visible light region having a wavelength of 380 nm or more, which causes the resin composition to be colored. There is. Therefore, it is preferable to use together with other ultraviolet absorbers.

  When used in combination with an ultraviolet absorber, among the ultraviolet absorbers, benzotriazoles that do not contain sulfur in the skeleton [1], triazoles that do not contain sulfur in the skeleton [2], and sulfur in the skeleton The ultraviolet absorber contained is labeled [3], for example, [1] and [2]; [1] and [3]; [2] and [3]: [1], [2] and [3] A combination of Furthermore, you may use [4] together with the ultraviolet absorber which does not correspond to any of [1]-[3].

  The light stabilizer is a compound that is said to have a function of capturing radicals generated mainly by oxidation by light. Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6 monotetraalkylpiperidine skeleton. Examples thereof include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (“ADEKA STAB LA-77Y” manufactured by ADEKA Corporation).

  A lubricant is a compound that is said to have an effect of improving mold releasability and workability by adjusting slippage between a polymer and a metal surface and preventing adhesion and adhesion. 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 preferred from the viewpoint of compatibility with the resin composition of the present invention. Examples include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and the like.

  When the resin composition of the present invention contains other polymer and / or additive, the methacrylic resin (A) may be added even when the methacrylic resin (A) and / or SMA resin (B) is polymerized. And it may add when mixing SMA resin (B), or may add after mixing methacryl resin (A) and 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, even more preferably 130 ° C. or higher, and most preferably 140 ° C. or higher. Further, the upper limit value of the glass transition temperature is more preferably 155 ° C. or less, and further preferably 150 ° C. or less. Generation | occurrence | production of the curvature under the high temperature of the molded object which consists of a resin composition of this invention can be suppressed because a glass transition temperature is the range of 115-160 degreeC.

  The saturated water absorption in 23 ° C. water of the resin composition of the present invention is preferably 1.9% by mass or less, more preferably 1.5% by mass or less, and 1.0% by mass or less. Is more preferable. When the saturated water absorption is 1.9% by mass or less, the resin composition of the present invention has excellent moisture resistance, and the 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 minutes. The lower limit value of MFR is more preferably 1.5 g / 10 min or more, and further preferably 2.0 g / 10 min. Further, the upper limit value of 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 minutes, the stability of heat-melt molding is good.

  The resin composition of the present invention is formed by extrusion molding methods such as co-extrusion molding, T-die lamination molding, and extrusion coating; insert injection molding, two-color injection molding, core back injection molding, sandwich injection molding, Various molded products can be obtained by heat-melt molding by an injection molding method such as an injection breath molding method; blow molding method; calendar molding method; press molding method; slush molding method. The resin composition of the present invention is also suitable for the production of molded products that require high temperature and long-term residence conditions because gels are unlikely to form even when melt molded for a long time at high temperatures. The resin composition of the present invention is suitable for production of thin and wide molded articles such as sheets, films, and plates.

[Laminate]
The laminate of the present invention has at least one layer composed of the resin composition of the present invention (hereinafter also referred to as resin composition [C1]) and at least one layer composed of another material. Other materials used for the laminate of the present invention are not particularly limited. Examples thereof include organic materials such as resins; inorganic materials such as simple metals and metal oxides.

  The laminated body which concerns on one Embodiment of this invention has at least 1 layer which consists of resin composition [C1] which is at least 1 layer which consists of resin composition [C1], and 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, ethylene-vinyl alcohol copolymer, polyacetal, and polyfluoride. Thermosetting of vinylidene chloride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin, polyether ether ketone, polysulfone, polyphenylene oxide, polyimide, polyetherimide, phenoxy resin; phenol resin, melamine resin, silicone resin, epoxy resin, etc. Energy ray-curable resin. Resin of resin composition [C2] can be used individually by 1 type or in combination of 2 or more types. Of these, thermoplastic resins are preferable, and polycarbonate is more preferable.

  When polycarbonate is employed as the resin, the amount of polycarbonate contained in the resin composition [C2] is preferably 90% by mass or more, more preferably 95% by mass or more, and 98% by mass or more. More preferably. The weight average molecular weight of the polycarbonate is preferably 20,000 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 a laminated sheet comprising the resin composition [C1] and the resin composition [C2] is obtained. It can be manufactured with excellent moldability and high productivity. The polycarbonate has a Mw / Mn of preferably 1.7 to 2.6, more preferably 1.7 to 2.3, and still more preferably 1.7 to 2.0.

  Commercially available products may be used as the polycarbonate. For example, “Caliver (registered trademark)” manufactured by Sumika Stylon Polycarbonate Co., Ltd., “Iupilon / Novalex (registered trademark)” manufactured by Mitsubishi Engineering Plastics Co., Ltd., Idemitsu Kosan Co., Ltd. “Taflon (registered trademark)” manufactured by Teijin Chemicals Ltd. and “Panlite (registered trademark)” manufactured by Teijin Chemicals Ltd. can be suitably 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 polycarbonate. Moreover, it is preferable that the glass transition temperature of resin composition [C2] is comparable as the glass transition temperature of resin composition [C1]. Specifically, the absolute value | ΔTg | 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 less, more preferably 20 ° C. or less. . When | ΔTg | is 30 ° C. or lower, 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 is preferably a thermoplastic resin composition (T) having a saturated water absorption rate of 0.1 to 1.0% by mass in 23 ° C. water. The thermoplastic resin composition (T) is preferably a resin composition containing polycarbonate. Moreover, it is preferable that the resin composition [C2] has the same saturated water absorption as that of the resin composition [C1]. Specifically, the absolute value | Δ saturated water absorption | of the difference between the saturated water absorption rate of the resin composition [C2] and the saturated water absorption rate of the resin composition [C1] is preferably 1.5% by mass or less. Is 1.0 mass% or less. When the saturated water absorption difference between the two resins is 1.5% by mass 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 is preferably a thermoplastic resin composition (T) having a melt volume rate (hereinafter referred to as “MVR”) in the range of 1 to ³⁰ cm 3/10 minutes. . The MVR is more preferably in the range of 3~20cm ^3/10 min, more preferably in the range of 6~10cm ^3/10 min.
In addition, MVR in this specification is measured using a melt indexer under conditions of a temperature of 300 ° C. and a load of 1.2 kg.

  The resin composition [C2] used in the present invention may contain a known additive in order to improve heat decomposition resistance, heat discoloration resistance, light resistance and the like. Additives include antioxidants, thermal degradation inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes and pigments, light diffusing agents, organic dyes , Matting agents, impact resistance modifiers, phosphors and the like.

  The laminate according to another embodiment of the present invention includes at least one layer [L1] composed of the resin composition [C1], at least one layer [L2] composed of the resin composition [C2], and at least one function. And a property-imparting layer [L3]. The functionality-imparting layer [L3] is not particularly limited. Examples thereof include 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, and an impact strength imparting layer. The functional 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, drying and curing. The antireflection layer can be obtained by laminating a low refractive index film and a high refractive index film by vapor deposition or the like. Of the functional layer [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 on the outermost side of the laminate. Provided. Only 1 type may be provided for functional provision layer [L3], and multiple types may be provided. From the viewpoint of enhancing the scratch resistance, the laminate of the present invention preferably has a scratch-resistant layer on at least one surface.

  The layer structure in the laminated body of the present invention is not particularly limited. As the stacking order of the laminate of the present invention, the layer made of the resin composition [C1] is the [L1] layer, the layer made of the resin composition [C2] is the [L2] layer, and the functional layer [L3] is 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, And L1] layer / [L2] layer / [L3] layer / [L2] layer / [L1] layer. For example, when the [L3] layer is a hard coat 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 are preferable.

  The present invention is useful in a laminate having a shape such as a sheet, a thin plate, and a film. When using the laminated body which concerns on this invention as a protective cover, it arrange | positions so that the resin composition [C1] layer may be located outside a resin composition [C2] layer seeing from the surface (protected surface) to be protected. It is preferable. For example, a laminate having a layer configuration of [L1] layer / [L2] layer may be arranged in the order of [L1] layer / [L2] layer / protected surface, or [L1] layer / [L2] layer / [ It is preferable to arrange the laminated body having the layer configuration of the L1 layer in the order of [L1] layer / [L2] layer / [L1] layer / protected surface.

  Although the total thickness of the laminated body according to the present invention can be set depending on the application, it is preferably 0.2 to 2 mm, more preferably 0.3 to 1.5 mm. If it is too thin, the rigidity tends to be insufficient. If it is too thick, it tends to hinder weight reduction of liquid crystal display devices.

  The thickness of the layer made of the resin composition [C1] in the laminate according to the present invention is preferably in the range of 0.02 to 0.5 mm. The lower limit value of the thickness of the layer is more preferably 0.03 mm or more, and further preferably 0.05 mm or more. Further, the upper limit value of the thickness of the 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 warpage at high temperatures, the laminate according to the present invention is preferably arranged in a lamination order that is symmetric in the thickness direction, and more preferably, the thickness of each layer is also symmetric. .

The laminate according to the present invention is not particularly limited by the production method, and can be produced by a multilayer molding method such as multilayer extrusion molding, multilayer blow molding, multilayer press molding, multicolor injection molding, insert injection molding, or the like. . Among these multilayer molding methods, multilayer extrusion molding of the resin composition [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 the production of multilayer laminates of thermoplastic resins is adopted, and includes, for example, a flat T die and a polishing roll having a mirror-finished surface. Molded by the machine. As a method of the T die, a heat-melted resin composition [C1] and a resin composition [C2] are laminated before the T die is flown, or a resin composition [C1] and a resin composition [C2]. ] Can be employed such as a multi-manifold system in which T is stacked inside the T-die. From the viewpoint of improving the smoothness of the interface between the layers constituting the laminate, the multi-manifold method is preferable.

The resin composition [C1] and the resin composition [C2] are preferably melt filtered through a filter before multilayer molding. By performing multilayer molding using each melt-filtered resin composition, a laminated sheet with few defects due to foreign matters, gels and the like can be obtained. The filter used for melt filtration is not particularly limited. The filter is appropriately selected from known ones in terms of operating temperature, viscosity, required filtration accuracy, and the like. Specific examples of the filter include nonwoven fabric made of polypropylene, cotton, polyester, viscose rayon, glass fiber, etc .; phenol resin impregnated cellulose film; metal fiber nonwoven fabric sintered film; metal powder sintered film; wire mesh; Can be mentioned. Among these, from the viewpoint of heat resistance, durability and pressure resistance, it is preferable to use a plurality of laminated metal fiber nonwoven fabric sintered films.
Although there is no restriction | limiting in particular in the filtration precision of the said filter, It is preferable that it is 30 micrometers or less, It is more preferable that it is 10 micrometers or less, It is further more preferable that it is 5 micrometers or less.

  According to the resin composition of the present invention, it has excellent transparency, surface hardness and heat resistance. Therefore, a molded product and a laminate obtained by melt-molding the resin composition according to the present invention have good appearance, excellent scratch resistance, and small dimensional change, and therefore can be suitably used for optical members and the like. it can.

  Examples of uses of the molded product, molded product and laminate according to the present invention include billboard components such as advertising towers, stand billboards, sleeve billboards, field billboards, and rooftop billboards; display components such as showcases, partition plates, and store displays. Fluorescent lamp cover, mood lighting cover, lamp shade, lighting parts such as light ceiling, light wall, chandelier; interior parts such as pendant and mirror; door, dome, safety window glass, partition, stair lumbar, balcony lumbar, for leisure Building parts such as roofs of buildings; aircraft windshields, pilot visors, motorcycles, motorboat windshields, bus shading plates, automotive side visors, rear visors, head wings, headlight covers, and other transportation equipment related parts; Nameplate, stereo cover, TV protection mask, vending machine display Electronic equipment parts such as covers; medical equipment parts such as incubators and X-ray parts; equipment-related parts such as machine covers, instrument covers, experimental devices, rulers, dials, observation windows; LCD protective plates, light guide plates, light guide films , Fresnel lenses, lenticular lenses, optical display parts such as front plates and diffusers for various displays; traffic-related parts such as road signs, guide boards, curved mirrors, and sound barriers; surface materials for automobile interiors, surface materials for mobile phones, Film members such as transparent conductive films, light guide films, polarizer protective films, marking films; members for household appliances such as canopy materials and control panels for washing machines, top panels for rice cookers; others, greenhouses, large tanks, boxes Aquarium, clock panel, bathtub, sanitary, desk mat, game parts, toy, mask for face protection when welding, etc. Door can be.

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

[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>
Using an injection molding machine (SE-180DU-HP, manufactured by Sumitomo Heavy Industries, Ltd.), the resin composition according to the present invention is injection molded under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 75 ° C., and a molding cycle of 1 minute. Thus, a square test piece having a thickness of 2 mm and a side of 50 mm was obtained. Each test piece was measured using a spectral color difference meter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the method of JIS-K7361-1.

<Haze>
A test piece made of the resin composition according to the present invention was obtained by the same method as described above. Each test piece was measured using a spectral color difference meter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. according to the method of JIS-K7361.

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

<Glass transition temperature (Tg)>
In accordance with JIS K7121, the resin composition according to the present invention was heated from room temperature to 250 ° C. at 20 ° C./min, held for 5 minutes, cooled to −100 ° C. at 10 ° C./min, and then −100 Differential scanning calorimetry (DSC) analysis was performed at a temperature condition where the temperature was raised from 10 ° C. to 250 ° C. at 10 / min. The midpoint glass transition temperature obtained from the DSC curve measured at the second temperature increase was adopted as the glass transition temperature in the present invention. TA-20 manufactured by TA INSTRUMENTS was used as a measuring device.

<Saturated water absorption>
A test piece made of the resin composition according to the present invention was obtained by the same method as described above. The test piece was vacuum-dried for 24 hours under the conditions of a temperature of 80 ° C. and 5 mmHg. The test piece was then allowed to cool in a desiccator. Immediately after removing the test piece from the desiccator, the mass (initial mass) was measured.
Subsequently, this test piece was immersed in 23 degreeC distilled water. The test piece was taken out of the water, the water adhering to the surface was wiped off, and the mass was measured. The test piece was immersed in distilled water, and the mass was measured in the same manner as described above. Immersion in distilled water and mass measurement were repeated until there was no change in mass. A saturated water absorption rate was calculated from the mass (water absorption mass) when the mass change disappeared and the initial mass by the following equation.
Saturated water absorption (%) = [(water absorption mass−initial mass) / initial mass] × 100

<Chemical resistance>
A test piece made of the resin composition according to the present invention was obtained by the same method as described above. The sunscreen agent 0.05g shown in Table 1 was uniformly apply | coated to the test piece surface, on it, the two attached white cloths for test (single fiber cloth), an aluminum plate (75 mm x 150 mm x 1 mm), and a weight (500 g) ) And allowed to stand at the temperature shown in Table 1 for 1 hour. Thereafter, the weight, the aluminum plate, and the attached test white cloth were removed, and the surface of the test piece was washed with a non-woven wiper (cotton seagull) soaked with a neutral detergent. After natural drying, the surface of the test piece was visually observed and evaluated according to the following criteria.
○: No change in appearance △: There is no attached white cloth trace, but slightly whitened ×: There is an attached white cloth trace, markedly whitened

<Examples of various materials>
For the methacrylic resin (A) and the vinyl copolymer (B) containing the resin composition according to the present invention, the following materials were used.
Methacrylic resin (A1): Kuraray Co., Ltd. parapet (Mw = 82,000, MMA copolymerization ratio = 100%, MA copolymerization ratio = 0%, rr ratio = 52%)
Methacrylic resin (A2): Parapet made by Kuraray Co., Ltd. (Mw = 120,000, MMA copolymerization ratio = 93.6%, MA copolymerization ratio = 6.4%, rr ratio = 48%)
Methacrylic resin (A3): Kuraray Parapet (Mw = 79,000, MMA copolymerization ratio = 88.7%, MA copolymerization ratio = 11.3%, rr ratio = 45%)
Vinyl copolymer (B): Resistive (Mw = 80,000, styrene / maleic anhydride / MMA = 56% / 18% / 26%) manufactured by Denki Kagaku Kogyo Co., Ltd.

<Example 1a>
70 parts by mass of methacrylic resin (A1) and 30 parts by mass of vinyl copolymer (B) were melt-kneaded at a cylinder temperature of 230 ° C. using a biaxial kneader. Thereafter, the molten resin was extruded to obtain a pellet-shaped resin composition [1]. The composition and properties of the resin composition [1] are shown in Table 2.

<Example 2a>
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 methacrylic resin (A1) and 50 parts by mass of vinyl copolymer (B). Table 2 shows the composition and physical properties of the resin composition [2].

<Example 3a>
Resin composition [3] was obtained in the same manner as in Example 1a except that the composition ratio of the resin composition was 30 parts by mass of methacrylic resin (A1) and 70 parts by mass of vinyl copolymer (B). Table 2 shows the composition and physical properties of the resin composition [3].

<Comparative Example 1a>
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].

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

<Comparative Example 4a>
Resin composition [7] was obtained in the same manner as in Example 1a except that methacrylic resin (A3) was used instead of methacrylic resin (A1). Table 2 shows the composition and physical properties of the resin composition [7].

<Comparative Example 5a>
Resin composition [8] was obtained in the same manner as in Example 2a, except that methacrylic resin (A3) was used instead of methacrylic resin (A1). Table 2 shows the composition and properties of the resin composition [8].

<Comparative Example 6a>
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 the above result showed, the resin composition (Examples 1a-3a) which concerns on this invention maintained transparency compared with the resin composition (Comparative Examples 1a-6a) which concerns on this invention of the same composition. Since it has a high glass transition temperature, surface hardness and low saturated water absorption, it has excellent heat resistance, scratch resistance and moisture resistance. Moreover, it is excellent in chemical resistance.

[Laminate] The physical 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 according to the present invention was measured using a spectral color difference meter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. according to the method of JIS-K7361-1. Further, the haze of the laminate according to the present invention was measured using an apparatus similar to the total light transmittance based on the method of JIS-K7361. ○ when the total light transmittance is 90% or more and haze is 0.3% or less, Δ when the total light transmittance is 90% or more or haze is 0.3% or less, and the total light transmittance is less than 90% And the thing whose haze exceeds 0.3% was made into x.

<Pencil hardness>
Measurement was performed using a table moving pencil scratch tester (model P) (manufactured by Toyo Seiki Co., Ltd.). The surface of the layer made of the resin composition of the laminate according to the present invention was checked for the presence of scratches on the scratch while pressing the pencil lead with a load of 750 g at an angle of 45 degrees. The hardness of the pencil lead increased in order, and the hardness of the lead that was one step softer than the point at which the scar was generated was taken as the pencil hardness. A pencil hardness of H or higher was evaluated as ◯, F was F, and a hardness of less than F was evaluated as X.

<War change amount>
From the laminate according to the present invention, a rectangular test piece having a short side of 65 mm and a long side of 110 mm is formed so that the direction perpendicular to the extrusion flow direction is the short side and the direction parallel to the extrusion flow direction is the long side. Cut out. After picking and hanging the short side of the test piece and leaving it in an environmental tester set at a temperature of 75 ° C. and a relative humidity of 50% for 4 hours, the test piece was allowed to cool to 25 ° C. Warped. This seems to be a warp caused by the influence of molding conditions. Place the test piece warped in a bow shape on the surface plate so that the end of the test piece is in contact with the surface plate (that is, the test piece is chevron-shaped), and the gap between the surface plate and the test piece is The maximum distance (usually, the vicinity of the center of the long side of the test piece is maximum) was measured using a gap gauge. This value was used as the initial warpage amount.
Subsequently, the short side of the bowed test piece was picked and hung and left in an environmental test machine set at a temperature of 85 ° C. and a relative humidity of 85% for 72 hours. The specimen was allowed to cool in an environmental testing machine set at 25 ° C. and 50% relative humidity for 4 hours, and then the maximum distance between the surface plate and the specimen was measured by the same method as described above. The difference between this measured value and the initial warpage amount was defined as “warpage change amount”. The absolute value of the amount of warp change was less than 0.5 mm, the case where the absolute value was less than 0.5 and less than 1.0 was Δ, and the case where the absolute value was 1.0 mm or more was x.

<Chemical resistance>
The laminate was cut into a square with a side of 50 mm and used as a test piece. The sunscreen agent 0.05g shown in Table 1 is uniformly apply | coated to the surface of the layer which consists of a resin composition of a test piece, Two sheets of attached white cloth (single fiber cloth) for a test on it, an aluminum plate (75 mm x 150 mm × 1 mm) and a weight (500 g) were placed and allowed to stand at the temperature shown in Table 1 for 1 hour. Thereafter, the weight, the aluminum plate, and the attached test white cloth were removed, and the surface of the test piece was washed with a non-woven wiper (cotton seagull) soaked with a neutral detergent. After natural drying, the surface of the test piece was visually observed and evaluated according to the following criteria.
○: No change in appearance △: There is no attached white cloth trace, but slightly whitened ×: There is an attached white cloth trace, markedly whitened

<Light resistance of polycarbonate layer>
A laminate test piece and a test piece of a single-layer film having a thickness of 80 μm of resin compositions [1] to [3] having no polycarbonate layer are irradiated with ultraviolet rays, and the color difference (ΔE) is determined according to JIS Z-8730. It was measured. The test piece of the laminate was irradiated with ultraviolet rays from the resin composition [1] to [3] layer side. A 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 method:
Testing machine: Iwasaki Electric Eye Super UV Tester SUV-F1 type colorimeter: Hitachi Color Analyzer C-2000 type Exposure time: 24 hours

<Example 1b>
Polycarbonate ("SD Polyca (registered trademark) PCX" manufactured by Sumika Stylon Polycarbonate Co., Ltd., the same shall apply hereinafter) to a single screw extruder [I] with a shaft diameter of 150 mm, set at a cylinder temperature of 245 to 260 ° C and a discharge rate of 430 kg / hour Of pellets were continuously charged. The pellets of the resin composition [1] were continuously charged into a single screw extruder [II] having a shaft diameter of 65 mm and a cylinder temperature of 215 to 230 ° C. and a discharge rate of 37 kg / hour.
A pleated cylindrical filter with a filter pore size of 20 μm (manufactured by Fuji Filter Industry Co., Ltd.), which is extruded from the extruder [I] and the extruder [II] simultaneously with the polycarbonate and the resin composition [1], and filled with the resin in advance. Is then introduced into the junction block, and then polycarbonate and resin composition [1] are co-extruded with a multi-manifold die (Nordson Co., Ltd.) having a resin discharge port width of 1600 mm and a lip interval of 2.0 mm at a temperature of 245 ° C. And made into a sheet. This sheet was formed into a bank between No. 1 and No. 2 rolls of four horizontal rolls, cooled while transferring the mirror surface with the four rolls, and a layer composed of a resin composition [1] having a thickness of 80 μm and a thickness. A laminate having a total thickness of 1000 μm and a layer made of 920 μm polycarbonate was obtained.

<Example 2b>
Except for changing the resin composition [1] to the resin composition [2], a layer composed of the resin composition [2] having a thickness of 80 μm and a layer composed of a polycarbonate having a thickness of 920 μm were prepared in the same manner as in Example 1b. A laminate having a total thickness of 1000 μm was obtained.

<Example 3b>
Except for changing the resin composition [1] to the resin composition [3], a layer composed of the resin composition [3] having a thickness of 80 μm and a layer composed of a polycarbonate having a thickness of 920 μm were prepared in the same manner as in Example 1b. A laminate having a total thickness of 1000 μm was obtained.

<Example 1c>
In Example 1b, a laminate was obtained in the same manner 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]. ΔE of the polycarbonate layer by UV irradiation was 15 or more in Example 1b, but 0.5 or less in Example 1c.
<Example 2c>
A laminate was obtained in the same manner as in Example 1c, except that the resin composition [2] was used. The ΔE of the polycarbonate layer was 15 or more in Example 2b, but 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 [3] was used. The ΔE of the polycarbonate layer was 15 or more in Example 3b, but 0.5 or less in Example 3c.

<Comparative Example 1b>
Except for changing the resin composition [1] to the resin composition [4], a layer composed of the resin composition [4] having a thickness of 80 μm and a layer composed of a polycarbonate having a thickness of 920 μm were prepared in the same manner as in Example 1b. A laminate having a total thickness of 1000 μm was obtained.

<Comparative Example 2b>
Except that the resin composition [1] was changed to the resin composition [5], a layer composed of the resin composition [5] having a thickness of 80 μm and a layer composed of a polycarbonate having a thickness of 920 μm were prepared in the same manner as in Example 1b. A laminate having a total thickness of 1000 μm was obtained.

<Comparative Example 3b>
Except for changing the resin composition [1] to the resin composition [6], a layer composed of the resin composition [6] having a thickness of 80 μm and a layer composed of a polycarbonate having a thickness of 920 μm were prepared in the same manner as in Example 1b. A laminate having a total thickness of 1000 μm was obtained.

<Comparative Example 4b>
Except for changing the resin composition [1] to the resin composition [7], a layer made of the resin composition [7] having a thickness of 80 μm and a layer made of a polycarbonate having a thickness of 920 μm were prepared in the same manner as in Example 1b. A laminate having a total thickness of 1000 μm was obtained.

<Comparative Example 5b>
Except for changing the resin composition [1] to the resin composition [8], a layer made of the resin composition [8] having a thickness of 80 μm and a layer made of a polycarbonate having a thickness of 920 μm were prepared in the same manner as in Example 1b. A laminate having a total thickness of 1000 μm was obtained.

<Comparative Example 6b>
Except for changing the resin composition [1] to the resin composition [9], a layer made of the resin composition [9] having a thickness of 80 μm and a layer made of a polycarbonate having a thickness of 920 μm were prepared in the same manner as in Example 1b. A laminate having a total thickness of 1000 μm was obtained.

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

As the above results show, the laminates (Examples 1b to 3b) according to the present invention have high pencil hardness and chemical resistance while maintaining transparency. Furthermore, it turns out that the laminated body which concerns on this invention has few curvature even if it is left to stand under high temperature and high humidity.

Claims (17)

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

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

(In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group.)   The resin composition according to claim 1, wherein the methacrylic resin (A) contains 99.5% by mass or more of a structural unit derived from methyl methacrylate.   The resin composition according to claim 1 or 2, wherein the methacrylic resin (A) has a syndiotacticity (rr) of triplet display of 50% or more.   The resin composition of any one of Claims 1-3 containing a methacryl resin (A) 30-60 mass% and a vinyl-type copolymer (B) 40-70 mass%.   The vinyl copolymer (B) contains 50 to 84% by mass of structural units derived from the aromatic vinyl compound (b1) and 15 to 49% by mass of structural units derived from the cyclic acid anhydride (b2). And the resin composition of any one of Claims 1-4 which contains 1-35 mass% of structural units derived from the methacrylic acid ester (b3).   The resin composition according to claim 5, wherein the methacrylic acid ester (b3) is methyl methacrylate.   Glass transition temperature is 115-160 degreeC, The resin composition of any one of Claims 1-6.   The resin composition of any one of Claims 1-7 containing a ultraviolet absorber.   The resin composition according to claim 8, wherein the ultraviolet absorber has a benzotriazole skeleton.   The resin composition according to claim 8, wherein the ultraviolet absorber has a triazine skeleton.   The said ultraviolet absorber contains sulfur in the frame | skeleton, The resin composition of any one of Claims 8-10 characterized by the above-mentioned.   The resin composition according to any one of claims 8 to 11, comprising two or more kinds of ultraviolet absorbers.   The molded article which comprises the resin composition of any one of Claims 1-12. A layer made of the resin composition according to any one of claims 1 to 12,
A laminate comprising a layer made of a thermoplastic resin composition (T) having a glass transition temperature in the range of 130 to 160 ° C.   The laminate according to claim 14, wherein the thermoplastic resin composition (T) is a resin composition containing polycarbonate.   The laminate according to claim 14 or 15, wherein an absolute value of a difference in Tg between the thermoplastic resin composition (T) and the resin composition is 30 ° C or less. The laminate according to any one of claims 14 to 16, further comprising a scratch-resistant layer on at least one surface.