JPWO2015050051A1 - Laminated body - Google Patents

Abstract

Provided is a laminate having a layer containing a methacrylic resin and a layer containing a polycarbonate, which is less likely to warp under high temperature and high humidity and has good impact resistance. SOLUTION: At least 45 to 90% by weight of methacrylic resin, a structural unit derived from an aromatic vinyl compound represented by the following general formula (a) and a structural unit derived from an acid anhydride represented by the following general formula (b) A layered product comprising: a layer comprising a resin composition containing 10 to 55% by mass of a copolymer comprising: and a layer comprising a polycarbonate. (In the formula: R1, R2, R3 and R4 each independently represents a hydrogen atom or an alkyl group.) [Selection] None

Description

  The present invention relates to a laminate comprising a layer containing a methacrylic resin and a layer containing a polycarbonate, which are less likely to warp under high temperature and high humidity and have good impact resistance.

  Methacrylic resin is excellent in transparency, scratch resistance, weather resistance and the like. On the other hand, polycarbonate is excellent in impact resistance. A laminate comprising a layer containing a methacrylic resin and a layer containing a polycarbonate is excellent in transparency, scratch resistance, weather resistance, impact resistance, etc., and is a wall of a house, furniture, home appliances, electronic equipment, display device. Used for surface members such as

  The above-mentioned laminate is likely to warp when exposed to high temperature and high humidity for a long time, which may cause a problem in the use environment. In order to solve this problem, a methyl methacrylate unit, a methacrylic acid unit, an acrylic acid unit, a maleic anhydride unit, an N-substituted or unsubstituted myreimide unit, a glutaric anhydride structural unit, and a glutarimide structural unit are selected. There is known a laminate including a layer made of a methacrylic resin having a glass transition temperature of 110 ° C. or higher and a layer made of polycarbonate (see Patent Document 1). However, such a laminate has a problem of low impact resistance as compared with a conventional laminate.

JP 2009-248416 A

  An object of the present invention is to provide a laminate comprising a layer containing a methacrylic resin and a layer made of polycarbonate, which is less likely to warp under high temperature and high humidity and has good impact resistance.

  In order to achieve the above-mentioned object, the present invention provides 45 to 90% by mass of a methacrylic resin and at least an aromatic vinyl compound represented by the following general formula (a) (hereinafter referred to as “aromatic vinyl compound (a)”). A copolymer (hereinafter referred to as “SMA resin”) and a structural unit derived from a structural unit derived from an acid anhydride represented by the following general formula (b) (hereinafter referred to as “acid anhydride (b)”) A laminate comprising: a layer composed of a resin composition (hereinafter referred to as “resin composition (1)”) containing 10 to 55% by mass; and a layer composed of polycarbonate.

（式中：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。）

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

（式中：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。）

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

  The laminate of the present invention is less likely to warp under high temperature and high humidity and has good impact resistance.

[Resin composition (1)]
The resin composition (1) will be described below.
The resin composition (1) contains a methacrylic resin and an SMA resin.
The content of the methacrylic resin in the resin composition (1) is in the range of 45 to 90% by mass, preferably in the range of 65 to 85% by mass, and more preferably in the range of 68 to 82% by mass. . When the content of the methacrylic resin in the resin composition (1) is 45% by mass or more, the laminate of the present invention has excellent transparency, scratch resistance, weather resistance, etc., and is 90% by mass or less. The occurrence of warpage under high temperature and high humidity can be suppressed.

The methacrylic resin is a resin containing a structural unit derived from a methacrylic acid ester.
Examples of the methacrylic acid ester include methyl methacrylate (hereinafter referred to as “MMA”), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, Methacrylic acid alkyl esters such as pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cyclohexane methacrylate heptyl, methacrylic acid cyclooctyl, methacrylic acid tricyclo [5.2.1.0 ^{2, 6]} dec-8-yl (hereinafter, referred to as "TCDMA") methacrylate consequent such Methacrylic acid aryl esters such as phenyl methacrylate; methacrylic acid aralkyl esters such as benzyl methacrylate; and the like, and MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate are preferred, and MMA is most preferred. The content of the structural unit derived from the methacrylic ester in the methacrylic resin is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and only the structural unit derived from the methacrylic ester. Also good.

  From the viewpoint of heat resistance, the methacrylic resin preferably contains 90% by mass or more of structural units derived from MMA, more preferably 95% by mass or more, and even more preferably 98% by mass or more. Only the structural unit derived from MMA may be used.

  The methacrylic resin may contain a structural unit derived from another monomer other than the methacrylic acid ester. Examples of such other monomers include methyl acrylate (hereinafter referred to as “MA”), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 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 is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less.

  The methacrylic resin can be obtained by polymerizing the above methacrylic acid ester and other monomers as optional components. In the case of using a plurality of types of monomers in such polymerization, usually, the 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.

The weight average molecular weight (hereinafter referred to as “Mw”) of the methacrylic resin is preferably 40,000 to 500,000. When the Mw is 40,000 or more, the laminate of the present invention has excellent scratch resistance and heat resistance, and when it is 500,000 or less, the resin composition (1) has excellent moldability. The productivity of the laminate of the present invention can be increased.
In addition, in this specification, Mw means the standard polystyrene conversion value measured using a gel perem chromatography (GPC).

  The content of the SMA resin in the resin composition (1) is in the range of 10 to 55% by mass, preferably in the range of 15 to 35% by mass, and more preferably in the range of 18 to 32% by mass. . In the laminate of the present invention, the occurrence of warpage under high temperature and high humidity can be suppressed when the content of the SMA resin in the resin composition (1) is 10% by mass or more, and the resistance is 55% by mass or less. Excellent impact.

  The SMA resin is a copolymer composed of at least a structural unit derived from the aromatic vinyl compound (a) and a structural unit derived from the acid anhydride (b).

Examples of the alkyl group that R ¹ and R ² in the general formula (a) and R ³ and R ⁴ in the general formula (b) 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 (a) in the SMA resin is preferably in the range of 50 to 85% by mass, more preferably 65 to 82% by mass, and 68 to 80% by mass. More preferably, it is in the range of%. When the content is in the range of 50 to 85% by mass, the compatibility between the SMA resin and the methacrylic resin is increased, and the resin composition (1) is excellent in transparency.

  Examples of the aromatic vinyl compound (a) include styrene; nuclear alkyl-substituted styrene 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 (a) may be used individually by 1 type, or may use multiple types together.

  The content of the structural unit derived from the acid anhydride (b) in the SMA resin is preferably in the range of 15 to 40% by mass, more preferably in the range of 18 to 35% by mass. More preferably, it is in the range of mass%. When the content is in the range of 15 to 40% by mass, the resin composition (1) is excellent in heat resistance and transparency.

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

  The SMA resin may have a structural unit derived from another monomer other than the aromatic vinyl compound (a) and the acid anhydride (b). Such other monomers include MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, methacrylic acid. Heptyl acid, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, benzyl methacrylate, phenyl methacrylate, etc. MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, te acrylate t-butyl, 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, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, acrylic Examples include acrylic acid esters such as toluyl acid, benzyl acrylate, isobornyl acrylate, and 3-dimethylaminoethyl acrylate. 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 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 can be obtained by polymerizing the aromatic vinyl compound (a), the acid anhydride (b), and other monomers as optional components. In such polymerization, a monomer mixture is usually prepared by mixing the monomers to be used, 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 is preferably in the range of 40,000 to 300,000. When the Mw is 40,000 or more, the laminate of the present invention has excellent scratch resistance and impact resistance. When the Mw is 300,000 or less, the resin composition (1) has excellent moldability. It is excellent and the productivity of the laminate of the present invention can be increased.

  The mass ratio of the methacrylic resin and the SMA resin (methacrylic resin / SMA resin) contained in the resin composition (1) is the suppression of the occurrence of warpage of the laminate under high temperature and high humidity, transparency, weather resistance, and impact resistance. In view of the above, it is preferably in the range of 45/55 to 90/10, more preferably in the range of 65/35 to 85/15, and still more preferably in the range of 68/32 to 82/18.

  The resin composition (1) is obtained by mixing the methacrylic resin and the SMA resin. For this mixing, 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, methacrylic resin and SMA resin are dissolved and mixed in an organic solvent such as toluene, tetrahydrofuran, or methyl ethyl ketone.

The resin composition (1) may contain a polymer other than the methacrylic resin and the SMA resin as long as the effects of the present invention are not impaired. Examples of such other polymers include polyolefins such as polyethylene and polypropylene, polyamides, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polyacetal, and other thermoplastic resins; phenol resins, melamine resins And thermosetting resins such as silicone resins and epoxy resins. These other polymers may be used individually by 1 type, or may use multiple types together.
The content of these other polymers in the resin composition (1) 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 (1) 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 not impairing 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 (1). The content of the ultraviolet absorber is 0.01 to 3 parts by mass, the content of the light stabilizer is 0.01 to 3 parts by mass, the content of the lubricant is 0.01 to 3 parts by mass, the content of the dye / pigment Is preferably 0.01 to 3 parts by mass.

  When the resin composition (1) contains other polymer and / or additive, it is added when the methacrylic resin and / or SMA resin is polymerized, or added when the methacrylic resin and SMA resin are mixed. Or you may add further, after mixing a methacryl resin and SMA resin.

The glass transition temperature of the resin composition (1) is preferably in the range of 120 to 160 ° C, more preferably in the range of 130 to 155 ° C, and still more preferably in the range of 140 to 150 ° C. When the glass transition temperature is in the range of 120 to 160 ° C., the occurrence of warpage of the laminate obtained in the present invention under high temperature and high humidity can be suppressed.
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 melt flow rate (hereinafter referred to as “MFR”) of the resin composition (1) is preferably in the range of 1 to 10 g / 10 minutes, more preferably in the range of 1.5 to 7 g / 10 minutes. 2 to 4 g / 10 min is more preferable. When the MFR is in the range of 1 to 10 g / 10 minutes, the stability of heat-melt molding is good.
In addition, MFR of the resin composition (1) in this specification is a value measured using a melt indexer at a temperature of 230 ° C. and a load of 3.8 kg.

[Polycarbonate]

  The polycarbonate used in the laminate of the present invention is preferably obtained by copolymerizing a dihydric phenol and a carbonate precursor.

  Examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl) cyclohexane. 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4- Hydroxyphenyl) sulfone and the like, and among them, bisphenol A is preferred. These dihydric phenols may be used individually by 1 type, or may use multiple types together.

  Examples of the carbonate precursor include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, and haloformates such as dihaloformates of dihydric phenols. These carbonate precursors may be used individually by 1 type, or may use multiple types together.

  The polycarbonate production method is not particularly limited. For example, an interfacial polymerization method in which an aqueous solution of a dihydric phenol and an organic solvent solution of a carbonate precursor are reacted at the interface, a dihydric phenol and a carbonate precursor are reacted at high temperature, reduced pressure, Examples thereof include a transesterification method in which the reaction is carried out under solvent conditions.

  Mw of the polycarbonate is preferably in the range of 10,000 to 100,000, and more preferably in the range of 20,000 to 70,000. When the Mw is 10,000 or more, the laminate of the present invention is excellent in impact resistance and heat resistance, and when it is 100,000 or less, the polycarbonate is excellent in molding processability and the production of the laminate of the present invention. Increases sex.

The polycarbonate may contain other polymers as long as the effects of the present invention are not impaired. As such another polymer, the same polymer as the other polymer that may be contained in the resin composition (1) can be used. These other polymers may be used individually by 1 type, or may use multiple types together.
The content of these other polymers in the polycarbonate is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.

  The polycarbonate may contain various additives as necessary. As an additive, the thing similar to the additive which the above-mentioned resin composition (1) may contain can be used. The content of these additives can be appropriately set within a range not impairing the effects of the present invention. The content of the antioxidant is 0.01 to 1 part by mass and the content of the ultraviolet absorber is 100 parts by mass of the polycarbonate. 0.01-3 parts by weight, light stabilizer content is 0.01-3 parts by weight, lubricant content is 0.01-3 parts by weight, dye / pigment content is 0.01-3 parts by weight Is preferred.

  When other polymers and / or additives are added to the polycarbonate, they may be added when copolymerizing the dihydric phenol and the carbonate precursor, or added and melted after the copolymerization is completed. You may knead.

  The glass transition temperature of the polycarbonate is preferably in the range of 130 to 160 ° C, more preferably in the range of 135 to 155 ° C, and further preferably in the range of 140 to 150 ° C. When the glass transition temperature is in the range of 130 to 160 ° C., the occurrence of warpage of the laminate of the present invention under high temperature and high humidity can be suppressed.

The MFR of the polycarbonate is preferably in the range of 1 to 30 g / 10 minutes, more preferably in the range of 3 to 20 g / 10 minutes, and further preferably in the range of 5 to 10 g / 10 minutes. When the MFR is in the range of 1 to 30 g / 10 min, the stability of heat-melt molding is good.
In addition, the MFR of polycarbonate in the present specification is measured using a melt indexer under conditions of a temperature of 300 ° C. and a load of 1.2 kg.

  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.

[Laminate]
The laminate of the present invention may have a plurality of layers made of the resin composition (1) and / or layers made of polycarbonate.

  The laminated body of this invention may have the layer (other resin layer) which consists of other resin besides the layer which consists of a resin composition (1), and the layer which consists of polycarbonate. Examples of the resin contained in the other resin layer include various thermoplastic resins other than the resin composition (1) and polycarbonate; thermosetting resin; energy ray curable resin; and the like.

  Examples of the other resin layers described above include an anti-scratch 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.

  These other resin layers may be one layer or plural. When there are a plurality of these other resin layers, they may be made of the same resin or different resins. In the laminate of the present invention, the arrangement order of the other resin layers is not particularly limited, and may be the surface or the inner layer.

  The thickness of the laminate of the present invention is preferably in the range of 0.03 to 5.0 mm, and preferably 0.05 to 4.0 mm from the viewpoint of manufacturing with good productivity while maintaining an excellent appearance. Is more preferable, and the range of 0.1 to 3.0 mm is more preferable.

  The thickness of the layer made of the resin composition (1) in the laminate of the present invention is preferably in the range of 0.01 to 0.5 mm, more preferably in the range of 0.015 to 0.3 mm. More preferably, it is in the range of 0.02 to 0.1 mm. When the thickness is less than 0.01 mm, scratch resistance and weather resistance may be insufficient. If it exceeds 0.5 mm, the impact resistance may be insufficient.

  The thickness of the layer made of polycarbonate in the laminate of the present invention is preferably in the range of 0.02 to 4.9 mm, more preferably in the range of 0.035 to 3.9 mm, and 0.08 to 2 More preferably, it is in the range of .9 mm. If the thickness is less than 0.02 mm, the impact resistance may be insufficient. Moreover, when it exceeds 4.9 mm, productivity may fall.

  When the laminate of the present invention has only a layer composed of the resin composition (1) and a layer composed of polycarbonate, the layer composed of the resin composition (1) is represented as (1), and the layer composed of polycarbonate as (2). As the stacking order of the laminate of the present invention, (1)-(2); (1)-(2)-(1); (2)-(1)-(2); (1)-(2 )-(1)-(2)-(1); and the like, and (1)-(2); (1)-(2)-(1); (1) from the viewpoint of enhancing the scratch resistance -(2)-(1)-(2)-(1); etc., it is preferable that at least one surface is laminated so as to be a layer composed of the resin composition (1).

Moreover, when the laminated body of this invention has another resin layer, when this other resin layer is described as (3), as a lamination | stacking order of the laminated body of this invention, (1)-(2) -(3); (3)-(1)-(2); (3)-(1)-(2)-(3); (3)-(1)-(2)-(1)-( 3); (1)-(2)-(3)-(2)-(1);
For example, when (3) is a scratch-resistant layer, the stacking order of the laminate of the present invention is (3 ′)-(1)-(2); 3 ′)-(1)-(2)-(3 ′), (3 ′)-(1)-(2)-(1)-(3 ′), etc., at least one surface becomes a scratch-resistant layer. It is preferable that they are laminated.

  When the laminate of the present invention has another resin layer different from (3) in addition to (3), the other resin layer different from (3) is represented as (4). In this case, the stacking order of the laminate of the present invention is (1)-(2)-(3)-(4); (4)-(3)-(1)-(2); (4)-( 3)-(1)-(2)-(3); (4)-(1)-(2)-(3); (4)-(3)-(1)-(2)-(3) -(4); (4)-(3)-(1)-(2)-(1)-(3)-(4);

  For example, when (3) is an anti-scratch layer and (4) is an antireflection layer, the antireflection layer is expressed as (4 ′), and (4 ′) − (3 ′) − (1) − ( 2); (4 ′)-(3 ′)-(1)-(2)-(3 ′); (4 ′)-(3 ′)-(1)-(2)-(3 ′)-( 4 ′); (4 ′)-(3 ′)-(1)-(2)-(1)-(3 ′)-(4 ′);

  From the viewpoint of suppressing the occurrence of warpage under high temperature and high humidity, it is preferable that the laminate of the present invention has a lamination order that is symmetrical in the thickness direction, and that the thickness of each layer is also symmetrical. preferable.

  Although there is no restriction | limiting in particular in the manufacturing method of the laminated body of this invention, Usually, it is preferable to laminate | stack the layer which consists of a resin composition (1), and the layer which consists of a polycarbonate by multilayer molding. Examples of multilayer molding include multi-layer extrusion molding, multilayer blow molding, multilayer press molding, multicolor injection molding, insert injection molding and the like, and multilayer extrusion molding is preferred from the viewpoint of productivity.

  As a method for further laminating other resin layers, a method of multilayer molding by the above-described method together with a layer made of the resin composition (1) and a layer made of polycarbonate, a layer made of the resin composition (1) prepared beforehand or a polycarbonate A method of applying another resin having fluidity to the surface of the layer made of the material and drying or curing, a method of pasting the layer made of the resin composition (1) prepared in advance or the surface of the polycarbonate through an adhesive layer, and the like. It is done.

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 can be preferably employed, and more preferably a flat T die and a surface with a mirror-finished polishing. Molded by an apparatus equipped with a roll.
In this case, the T-die method is a feed block method in which the resin composition (1) and polycarbonate in a heated and melted state are laminated before inflow of the T-die, and the resin composition (1) and polycarbonate are laminated inside the T-die. A multi-manifold system can be used. 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 (1) and the polycarbonate are preferably melt-filtered through a filter before multilayer molding. By multilayer molding using each melt-filtered resin composition, a laminate with few defects due to foreign matters and gels can be obtained. The filter medium used is not particularly limited, and is appropriately selected depending on the operating temperature, viscosity, and filtration accuracy. For example, nonwoven fabric made of polypropylene, cotton, polyester, rayon, glass fiber, etc .; phenol resin-impregnated cellulose film; Bonded film; metal powder sintered film; wire mesh; or a combination thereof. Among these, from the viewpoint of heat resistance and durability, 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.

Hereinafter, the scratch-resistant layer will be described in detail as an example of a layer made of another resin composition.
In the present specification, the scratch-resistant layer means a layer exhibiting a hardness of “3H” or higher in a pencil scratch test defined by JIS-K5600-5-4. A layer having a hardness of “4H” or more is preferable. The scratch-resistant layer is preferably provided on the surface of the layer made of the resin composition (1).

  The thickness of the scratch-resistant layer is preferably 2 to 10 μm, more preferably 3 to 8 μm, and still more preferably 4 to 7 μm. When the thickness is 2 μm or more, scratch resistance tends to be maintained, and when the thickness is 10 μm or less, the impact resistance of the laminate tends to be excellent.

  The scratch-resistant layer is usually obtained by applying a fluid curable composition comprising a monomer, oligomer, resin, etc. to the surface of another layer (for example, a layer comprising a resin composition (1) or a layer comprising a polycarbonate) It can be formed by curing. These curable compositions are, for example, thermosetting compositions that are cured by heat and energy beam curable compositions that are cured by energy beams such as electron beams, radiation, and ultraviolet rays.

Examples of the thermosetting composition include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon Examples thereof include a composition containing a resin, a polysiloxane resin and the like.
These thermosetting compositions may contain, for example, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, and the like as necessary. As the curing agent, isocyanate, organic sulfonic acid and the like are usually used for polyester resins and polyurethane resins, amine is epoxy resin, peroxide such as methyl ethyl ketone peroxide, radical initiator such as azobisisobutyl ester. Used for unsaturated polyester resins.

  Examples of the energy ray curable composition include a composition containing an oligomer and / or a monomer having a polymerizable unsaturated bond such as an acryloyl group or a methacryloyl group, a thiol group, or an epoxy group in the molecule. From the viewpoint of enhancing the scratch resistance, a composition containing an oligomer and / or monomer having a plurality of acryloyl groups or methacryloyl groups is preferred.

  The energy beam curable composition may contain a photopolymerization initiator and / or a photosensitizer. Examples of such photopolymerization initiators include carbonyl compounds such as benzoin methyl ether, acetophenone, 3-methylacetophenone, benzophenone and 4-chlorobenzophenone; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; -Trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, etc. are mentioned, and examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine and the like.

  In the curable composition, the content of these curable compounds is preferably in the range of 30 to 100% by mass, more preferably in the range of 40 to 95% by mass, and in the range of 50 to 95% by mass. More preferably it is. These curable compounds may be used alone or in combination of two or more.

  The curable composition may be a monofunctional monomer; an organic solvent; a leveling agent, an antiblocking agent, a dispersion stabilizer, an ultraviolet absorber, a light stabilizer, an antioxidant, an antifoaming agent, a thickener, if necessary. An additive such as a lubricant, an antistatic agent, an antifouling agent, an antifogging agent, a filler, and a catalyst may be appropriately contained. The content of these additives can be appropriately set as long as the effects of the present invention are not impaired.

  Examples of the coating method for the curable composition include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, and screen printing. Is mentioned.

EXAMPLES Hereinafter, although an Example etc. demonstrate this invention in detail, this invention is not limited to these.
The resin compositions obtained in the production examples described later, the laminates obtained in the examples and comparative examples, and the sheets obtained in the reference examples were evaluated by the following methods.

〔Glass-transition temperature〕
The sheet obtained in the reference example was dried under reduced pressure (1 kPa) at 80 ° C. for 24 hours, then a 10 mg test piece was cut out and sealed with an aluminum pan, and a differential scanning calorimeter (“DSC-50”, stock After making nitrogen substitution for 30 minutes or more using a company Rigaku), the temperature was raised from 25 ° C. to 200 ° C. at a rate of 20 ° C./minute in a nitrogen stream of 10 ml / min, and held for 10 minutes. Cooled to 25 ° C. (primary scan). Next, the temperature was raised to 200 ° C. at a rate of 10 ° C./min (secondary scanning), and the glass transition temperature was calculated by the midpoint method.

[Saturated water absorption]
A test piece prepared by cutting the sheet obtained in Reference Example into a square with a side of 50 mm was dried under reduced pressure (1 kPa) at 80 ° C. for 24 hours, and then allowed to cool in a desiccator at a temperature of 23 ° C. and a relative humidity of 50%. After that, the mass was promptly measured to obtain the initial mass. Then, the test piece was immersed in distilled water at 23 ° C., the mass was measured over time, and the saturated water absorption rate was calculated by the following formula using the mass (water absorption mass) when no mass change was observed.
Saturated water absorption (%) = [(water absorption mass−initial mass) / initial mass] × 100

(Impact resistance)
The sheets obtained in Reference Examples and the laminates obtained in Examples and Comparative Examples were cut into rectangles having a short side of 70 mm and a long side of 110 mm, respectively, to prepare test pieces. About the laminated body of the Example and the comparative example, the short side was cut out in the direction perpendicular | vertical to an extrusion flow direction, and the long side was cut out in the parallel side. Next, on the pedestal having a rectangular opening having a short side of 50 mm and a long side of 90 mm, the long side and the short side of the opening of the test piece and the pedestal are respectively parallel, and the center of the test piece and the center of the opening Were fixed with double-sided tape so that they matched. Under the present circumstances, about the test piece produced from the laminated body obtained by the Example and the comparative example, it fixed so that the base and the layer which consists of a polycarbonate might oppose.
Next, a steel ball having a diameter of 30 mm and a mass of 112 g was freely dropped from the vertical height of 10 cm at the center of the test piece, and the presence or absence of appearance changes such as dents, cracks, fractures, cloudiness, and whitening was observed with the naked eye. Further, the height at which the steel ball is allowed to freely fall is increased by 10 cm, and the same observation is repeated. The height at which the appearance change is made −10 cm, that is, the highest height at which the appearance change has not occurred is set as the impact resistance. Recorded as an indicator.

[Total light transmittance]
The laminates of Examples and Comparative Examples were measured using a spectral color difference meter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. according to the method described in JIS-K7361.

[Change in warpage under high temperature and high humidity]
The laminates of Examples and Comparative Examples were cut into rectangles such that the direction perpendicular to the extrusion flow direction was the short side and the direction parallel to the extrusion flow direction was the long side, and the short side was 30 mm and the long side was 150 mm. After the test pieces were prepared, the test pieces were left for 72 hours in an environment at a temperature of 23 ° C. and a relative humidity of 50%. As a result, all the test pieces were layered with the resin composition (1) along the long side (or its The methacrylic resin (A), resin composition (1 ′), or methacrylic resin (X) layer used instead was used as the outer layer, and the polycarbonate layer was used as the inner layer. On the surface plate, both ends of the test piece having such bow-shaped warpage are in contact with the surface plate (that is, the test piece has an upward convex shape, and the layer made of the resin composition (1) is made of polycarbonate on the upper side. When the maximum value of the gap between the test piece and the surface plate was measured using a gap gauge, the value was taken as the initial amount of warpage.
Next, a test piece having a short side fixed with a clip was suspended in an environmental test machine set at a temperature of 85 ° C. and a relative humidity of 85%, and left in that state for 24 hours. Then, it stood to cool to 23 degreeC, the maximum value of the clearance gap between a test piece and a surface plate was measured by the same method, and the difference with the initial curvature amount was evaluated as curvature variation | change_quantity under high temperature, high humidity.

[Pencil scratch hardness]
Measurement was performed using a table moving pencil scratch tester (model P) (manufactured by Toyo Seiki Co., Ltd.). The layer (or the methacrylic resin (A), the resin composition (1 ′), or the methacrylic resin (X) used instead of the layered resin composition (1) obtained in Examples and Comparative Examples. The presence or absence of scratches on the scratch was confirmed while pressing the pencil lead with an angle of 45 degrees and a load of 750 g with respect to the surface of the layer. 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 scratch hardness.

(Production Example 1)
20 parts by mass of SMA resin (manufactured by POLYSCOPE, trade name: XIRAN26080, maleic anhydride content 26% by mass) and 80 parts by mass of methacrylic resin (MMA and MA at a mass ratio of 98.9: 1.1 by radical polymerization) A random copolymerized copolymer, Mw = 90,000, hereinafter referred to as “methacrylic resin (A)”, the composition of which is shown in Table 2) is supplied to the hopper of a twin screw extruder and melted at a cylinder temperature of 230 ° C. The mixture was kneaded and extruded to obtain a pellet-shaped resin composition (hereinafter referred to as “resin composition (1-1)”). The composition is shown in Table 1. The MFR of the resin composition (1-1) measured at a temperature of 230 ° C. under a load of 3.8 kg using a melt indexer was 3.2 g / 10 minutes.

(Production Example 2)
30 parts by mass of SMA resin (manufactured by POLYSCOPE, trade name: XIRAN26080, maleic anhydride content 26% by mass) and 70 parts by mass of methacrylic resin (A) were supplied to the hopper of the twin screw extruder, and the cylinder temperature was 230 ° C. The mixture was melt-kneaded and extruded to obtain a pellet-shaped resin composition (hereinafter referred to as “resin composition (1-2)”). The composition is shown in Table 1. The MFR of the resin composition (1-2) measured at a temperature of 230 ° C. under a load of 3.8 kg using a melt indexer was 3.4 g / 10 minutes.

(Production Example 3)
30 parts by mass of SMA resin (manufactured by POLYSCOPE, trade name: XIRAN 23110, maleic anhydride content 23% by mass) and 70 parts by mass of methacrylic resin (A) were supplied to the hopper of the twin screw extruder, and the cylinder temperature was 230 ° C. The mixture was melt-kneaded and extruded to obtain a pellet-shaped resin composition (hereinafter referred to as “resin composition (1-3)”). The composition is shown in Table 1. The MFR of the resin composition (1-3) measured at 230 ° C. under a load of 3.8 kg using a melt indexer was 2.6 g / 10 minutes.

(Production Example 4)
50 parts by mass of SMA resin (manufactured by POLYSCOPE, trade name: XIRAN26080, maleic anhydride content 26% by mass) and 50 parts by mass of methacrylic resin (A) were supplied to the hopper of the twin screw extruder, and the cylinder temperature was 230 ° C. The mixture was melt-kneaded and extruded to obtain a pellet-shaped resin composition (hereinafter referred to as “resin composition (1-4)”). The composition is shown in Table 1. The MFR of the resin composition (1-4) measured at 230 ° C. under a load of 3.8 kg using a melt indexer was 3.8 g / 10 min.

(Production Example 5)
70 parts by mass of SMA resin (manufactured by POLYSCOPE, trade name: XIRAN26080, maleic anhydride content 26% by mass) and 30 parts by mass of methacrylic resin (A) were supplied to the hopper of the twin screw extruder, and the cylinder temperature was 230 ° C. Were melt-kneaded and extruded to obtain a pellet-shaped resin composition (hereinafter referred to as “resin composition (1 ′)”). The composition is shown in Table 1. The MFR of the resin composition (1 ′) measured at 230 ° C. under a load of 3.8 kg using a melt indexer was 4.5 g / 10 min.

(Production Example 6)
63 parts by weight MMA, 35 parts by weight TCDMA, 2 parts by weight MA, 0.06 parts by weight azobisisobutyronitrile, 0.01 parts by weight 1,1-bis (t-butylper Oxy) cyclohexane, a monomer mixture composed of 0.2 parts by mass of normal octyl mercaptan, water, a dispersant stabilizer, a pH adjuster and the like were added. The autoclave was heated to 70 ° C. with stirring, stirred at 70 ° C. for 150 minutes, and then held at 120 ° C. for 60 minutes for polymerization. The polymerization reaction liquid was cooled to room temperature, solid content was separated by filtration, washed with water, and dried in hot air at 80 ° C. for 24 hours. Next, the solid content was supplied to a hopper of a twin screw extruder, melt kneaded at a cylinder temperature of 230 ° C., and extrusion molded to obtain a pellet-shaped methacrylic resin (hereinafter referred to as “methacrylic resin (X)”). The resin composition is shown in Table 2. The MFR of the methacrylic resin (X) measured under a load of 3.8 kg at a temperature of 230 ° C. using a melt indexer was 2.1 g / 10 min.

[Example 1]
A single screw extruder with a shaft diameter of 50 mm is made of polycarbonate (“Caliver 300-8” manufactured by Sumika Stylon Polycarbonate Co., Ltd., Mw = 50,000, glass transition temperature = 150 ° C., temperature 300 ° C., MFR under 1.2 kg load) = 6.7 g / 10 min) was continuously added and extruded in a molten state under the conditions of a cylinder temperature of 280 ° C. and a discharge rate of 30 kg / hour. On the other hand, pellets of the resin composition (1-1) were continuously charged into a single screw extruder having a shaft diameter of 30 mm, and extruded in a molten state under conditions of a cylinder temperature of 220 ° C. and a discharge rate of 2 kg / hour. The molten polycarbonate and the resin composition (1-1) are introduced into a junction block, laminated with a multi-manifold die set at 250 ° C., extruded into a sheet, and a resin composition (1- A laminate having a thickness of 1000 μm formed from two layers of a layer consisting of 1) and a layer consisting of a polycarbonate having a thickness of 940 μm was produced. Table 3 shows the evaluation results of the laminate.

[Example 2]
A laminate was produced in the same manner as in Example 1 except that the resin composition (1-2) was used instead of the resin composition (1-1) in Example 1. Table 3 shows the evaluation results of the laminate.

Example 3
A laminate was prepared in the same manner as in Example 1 except that the resin composition (1-3) was used instead of the resin composition (1-1) of Example 1. Table 3 shows the evaluation results of the laminate.

Example 4
A laminate was produced in the same manner as in Example 1 except that the resin composition (1-4) was used instead of the resin composition (1-1) of Example 1. Table 3 shows the evaluation results of the laminate.

[Comparative Example 1]
A laminate was prepared in the same manner as in Example 1 except that the methacrylic resin (A) was used instead of the resin composition (1-1) in Example 1. Table 3 shows the evaluation results of the laminate.

[Comparative Example 2]
A laminate was produced in the same manner as in Example 1 except that the resin composition (1 ′) was used instead of the resin composition (1-1) in Example 1. Table 3 shows the evaluation results of the laminate.

[Comparative Example 3]
A laminate was prepared in the same manner as in Example 1 except that the methacrylic resin (X) was used instead of the resin composition (1-1) in Example 1. Table 3 shows the evaluation results of the laminate.

[Reference Example 1]
The resin composition (1-1) is placed in a rectangular mold frame having a short side of 110 mm and a long side of 150 mm, and pressed at 180 ° C. and 50 kg / cm ² for 5 minutes, and has a thickness of 3 mm and a short side of 110 mm. A sheet having a long side of 150 mm was produced. Table 4 shows the evaluation results of the sheet.

[Reference Example 2]
A sheet was produced in the same manner as in Reference Example 1 except that the resin composition (1-1) was replaced with the resin composition (1-2). Table 4 shows the evaluation results of the sheet.

[Reference Example 3]
A sheet was produced in the same manner as in Reference Example 1 except that the resin composition (1-1) was replaced with the resin composition (1-3). Table 4 shows the evaluation results of the sheet.

[Reference Example 4]
A sheet was produced in the same manner as in Reference Example 1 except that the resin composition (1-1) was replaced with the resin composition (1-4). Table 4 shows the evaluation results of the sheet.

[Reference Example 5]
A sheet was produced in the same manner as in Reference Example 1 except that the resin composition (1-1) was replaced with the methacrylic resin (A). Table 4 shows the evaluation results of the sheet.

[Reference Example 6]
A sheet was produced in the same manner as in Reference Example 1 except that the resin composition (1-1) was replaced with the resin composition (1 ′). Table 4 shows the evaluation results of the sheet.

[Reference Example 7]
A sheet was produced in the same manner as in Reference Example 1 except that the resin composition (1-1) was replaced with the methacrylic resin (X). Table 4 shows the evaluation results of the sheet.

Sheets (Reference Examples 1 to 4 and 6) made of the resin composition (1) or the resin composition (1 ′) used in the laminate of the present invention are sheets made of methacrylic resin (X) copolymerized with TCDMA (reference) Similar to Example 7), the glass transition temperature is higher and the saturated water absorption is lower than that of the sheet made of methacrylic resin (A) (Reference Example 5). It is presumed that the high glass transition temperature and low saturated water absorption rate of the sheet made of the resin composition (1) are caused by the suppression of the occurrence of warpage of the laminate of the present invention under high temperature and high humidity.
On the other hand, the sheet | seat (reference examples 1-4, 6) which consists of resin composition (1) or (1 ') is from methacrylic resin (A) similarly to the sheet | seat (reference example 7) which consists of methacrylic resin (X). The impact resistance is reduced as compared with the sheet (Reference Example 5).
However, in the laminates of the present invention shown in Table 3 (Examples 1 to 4), a laminate (comparative example) using a methacrylic resin (A) which is a general methacrylic resin instead of the resin composition (1). Compared with 1), the amount of change in warping is significantly less, and the impact resistance is hardly lowered. Furthermore, surprisingly, the laminates of Examples 1 to 3 among the laminates of the present invention show no reduction in impact resistance. Further, the total light transmittance and the pencil scratch hardness are equivalent to those of Comparative Example 1.
On the other hand, instead of the resin composition (1), a laminate (Comparative Example 2) using a resin composition (1 ′) having a higher SMA resin content or a methacrylic resin (X) was used. Compared with the laminated body (Comparative Example 1) using the methacrylic resin (A), the laminated body (Comparative Example 3) has a significantly reduced impact resistance.
As described above, the laminate of the present invention can improve the amount of change in warpage without degrading various performances of the conventional laminate of methacrylic resin (A) and polycarbonate.

  The laminate of the present invention is characterized in that it is less likely to warp under high temperature and high humidity and has excellent impact resistance, and is suitable for use on the surface of a display device or the like.

Claims (3)

A co-polymer comprising 45 to 90% by mass of a methacrylic resin and at least a structural unit derived from an aromatic vinyl compound represented by the following general formula (a) and a structural unit derived from an acid anhydride represented by the following general formula (b). A laminate comprising: a layer made of a resin composition containing 10 to 55% by mass of a polymer; and a layer made of polycarbonate.

(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 represents a hydrogen atom or an alkyl group.)
  The copolymer contains 50 to 85% by mass of structural units derived from the aromatic vinyl compound (a) and 15 to 40% by mass of structural units derived from the acid anhydride (b). The laminate according to claim 1.   The laminate according to claim 1 or 2, further comprising a scratch-resistant layer on at least one surface.