KR102365229B1 - Process for producing extruded resin sheet, and extruded resin sheet - Google Patents

Abstract

The present invention provides a method for manufacturing a resin plate having good surface properties and suppressed occurrence of warpage due to residual stress. The difference between the coefficient of linear expansion (S1) of the polycarbonate-containing layer and the coefficient of linear expansion (S2) of the methacrylic resin-containing layer and the ratio of the coefficient of linear expansion of the polycarbonate-containing layer ((S2 - S1)/S1) are -10% to +5%, , the glass transition temperature of the methacrylic resin-containing layer is 120 to 160°C. A thermoplastic resin laminate (resin plate 16) in which a polycarbonate-containing layer and a methacrylic resin-containing layer are laminated is extruded from a T die 11 in a molten state, and between the first and second cooling rolls 12 and 13 After being pinched|interposed and wound around the 2nd cooling roll 13, it is wound around the 3rd cooling roll 14, and it cools, and takes it up with the take-up roll 15. The position where the resin plate 16 peels from the 3rd cooling roll 14 WHEREIN: Let the temperature of whole resin be the range of 0 degreeC - +15 degreeC with respect to the glass transition temperature of a polycarbonate containing layer.

Description

The manufacturing method of an extruded resin board, and an extruded resin board

The present invention relates to a resin plate. More specifically, the present invention is provided with a layer containing a methacrylic resin suitable for a protective cover of a touch panel, etc. and a layer containing polycarbonate having good surface properties and suppressed occurrence of warpage due to residual stress. It relates to a method for manufacturing a resin plate.

A touch panel (or a touch screen) is the electronic component which combined the display device and the position input device. Electronic devices can be operated by touching the touch panel with a finger or a pen. Touch panels are used in ATMs of financial institutions such as banks, vending machines, mobile phones, personal digital assistants (PDAs), digital audio players, portable game machines, tablet-type personal computers, photocopiers, fax machines, and digital information devices such as car navigation systems. .

An input operation by the touch panel may cause scratches on the surface or crush the inside. In order to prevent this, a transparent protective cover is installed on the surface of the touch panel. As a protective cover, a thing made of tempered glass is mainly used. Moreover, development of the transparent resin protective cover is implemented from a viewpoint of workability and weight reduction. Gloss, abrasion resistance, impact resistance, etc. are calculated|required of this protective cover.

By the way, polycarbonate is one of resin suitable for obtaining the molded article excellent in impact resistance. A methacrylic resin is one of the resins suitable for obtaining the molded article excellent in high glossiness and abrasion resistance. In addition, by heat-melting molding (for example, co-extrusion molding) of polycarbonate and a methacryl resin simultaneously, the resin board which consists of a layer which consists of a polycarbonate and a layer which consists of a methacryl resin can be manufactured. In the hot melt molding of such a resin plate, a considerable amount of strain stress remains in the molded article obtained due to the difference in the characteristics of the two types of resin. The deformation stress remaining in this molded article is called residual stress, and the molded article having the residual stress generates warpage or shrinkage by heat or the like.

In a plate-shaped molded article such as the above-mentioned resin plate, in particular, warpage resulting from residual stress becomes a problem. As one of the methods of reducing the residual stress in a plate-shaped molded article and suppressing generation|occurrence|production of curvature, the method by adjusting the rotation speed of the cooling roll used for extrusion molding is known (for example, refer patent document 1).

Moreover, in order to solve this problem, the improvement of the heat resistance and moisture resistance of a methacryl resin is examined. For example, it is selected from a methyl methacrylate unit, a methacrylic acid unit, an acrylic acid unit, a maleic anhydride unit, an N-substituted or unsubstituted maleimide unit, a glutaric anhydride structural unit, and a glutarimide structural unit. It has a unit and a glass transition temperature of 110°C or higher is used to form a first layer using a methacrylic resin, and a two-layered resin plate having a layer made of polycarbonate is reported (for example, Patent Document 2) Reference). However, such a resin board is still insufficient in the heat resistance and moisture resistance of a methacrylic resin, and even if it uses this, it does not lead to the sufficient solution of the above-mentioned problem.

Moreover, in order to solve such a problem, the method of paying attention to making small the difference of the coefficient of linear expansion between two resin sheets, and controlling generation|occurrence|production of curvature is also known (for example, refer patent document 3). However, the above-mentioned problem was not solvable only by achieving the regulation of the coefficient of linear expansion.

Japanese Patent Laid-Open No. 2007-185956 Japanese Patent Application Laid-Open No. 2009-248416 Japanese Patent Laid-Open No. 2007-118597

In the resin plate, the degree of the stress remaining in each resin layer is different. For this reason, reducing the residual stress by adjustment of the rotation speed of the cooling roll used for extrusion molding is attempted. However, when a molded article is detached from a cooling roll, a stripe-like defect called chatter mark may generate|occur|produce on the surface of a molded article, and surface property may fall. This becomes a subject in using the resin board for the protective cover of a touchscreen etc.

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin plate and a method for manufacturing a resin plate in which surface properties are good and occurrence of warpage due to residual stress is suppressed.

MEANS TO SOLVE THE PROBLEM The present inventors discovered this invention containing the following aspects, as a result of examining in order to achieve the said objective.

That is, the present invention includes the following aspects.

One aspect of the method for producing an extruded resin plate according to the present invention (hereinafter, “extruded resin plate” is appropriately referred to as “resin plate”) is a layer containing a methacrylic resin on one side of a layer containing polycarbonate. As a manufacturing method of the laminated|stacked extruded resin board, the following process is implemented.

A process of extruding a thermoplastic resin laminate in which a layer containing a methacrylic resin is laminated on one side of a layer containing polycarbonate in a molten state from a T-die.

A step of sandwiching the thermoplastic resin laminate between the first cooling roll and the second cooling roll.

After winding the said thermoplastic resin laminated body on the said 2nd cooling roll, the process of cooling by winding it around a 3rd cooling roll.

The process of taking up the said thermoplastic resin laminated body with a take-up roll.

In addition, in each process mentioned above, the following requirements are satisfy|filled.

The difference (S2 - S1) between the coefficient of linear expansion (S1) of the layer containing the polycarbonate and the coefficient of linear expansion (S2) of the layer containing the methacrylic resin, and the coefficient of linear expansion of the layer containing the polycarbonate (S1) ratio ((S2-S1)/S1) of -10% to +5%. Hereinafter, the ratio ((S2 - S1)/S1) is appropriately described as "linear expansion ratio (SR)".

The glass transition temperature of the layer containing the said methacrylic resin shall be 120-160 degreeC.

At the position where the thermoplastic resin laminate is peeled off from the third cooling roll, the temperature of the entire resin is in the range of 0°C to +15°C with respect to the glass transition temperature (Tg) of the polycarbonate.

By satisfying these requirements, it becomes possible to realize a resin plate having good surface properties and small warpage resulting from residual stress.

Moreover, in one aspect of the resin board obtained by the manufacturing method of the above-mentioned extruded resin board, the layer containing the said methacrylic resin contains 40-80 mass % of structural units derived from methyl methacrylate, and the following general It is preferable to contain 20-60 mass % of structural units derived from the methacrylic acid ester represented by Formula (I).

[Formula 1]

(In the formula, Cy represents an alicyclic hydrocarbon group.)

Moreover, it is more preferable that Cy in general formula (I) is a polycyclic aliphatic hydrocarbon group.

Moreover, one aspect of the resin board obtained by the manufacturing method of the above-mentioned extruded resin board is less than 80 mass % of methacryl resin in the layer containing the said methacryl resin, and the aromatic vinyl compound represented by at least following General formula (II) It is preferable to contain 20 mass % or more of the copolymer which consists of a structural unit derived from a structural unit derived from and the structural unit derived from an acid anhydride represented by the following general formula (III).

[Formula 2]

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

[Formula 3]

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

Moreover, the said copolymer contains 50-84 mass % of the structural unit derived from the said aromatic vinyl compound, contains 15-49 mass % of the structural unit derived from the said acid anhydride, 1-25 mass % of methacrylic acid ester monomers It is preferable to contain by mass %, and it is still more preferable that said methacrylic acid ester monomer is methyl methacrylate.

It is preferable that the above-mentioned resin board further equips at least one surface with an abrasion-resistant layer.

The resin plate of this invention has favorable surface property, and generation|occurrence|production of the curvature resulting from residual stress is suppressed. Moreover, the resin board of this invention is suitable for a touch panel protective cover by which glossiness, abrasion resistance, and impact resistance are calculated|required, for example.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the manufacturing method of the resin plate by co-extrusion which concerns on one Embodiment of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described with reference to drawings. For clarity of explanation, the following description and drawings are appropriately omitted and simplified. In each figure, the same code|symbol is attached|subjected to the component which has the same structure or function, and an equivalent part, and the description is abbreviate|omitted.

Embodiment 1

The resin plate according to the present invention is a layer containing a methacrylic resin on one side of a polycarbonate-containing layer (hereinafter, appropriately, also referred to as a "polycarbonate-containing layer") (hereinafter, appropriately, also referred to as a "methacrylic resin-containing layer") described) are stacked.

When the layer containing a methacrylic resin is laminated|stacked on the layer containing polycarbonate, it is excellent in transparency, impact resistance, and abrasion resistance.

A resin plate is excellent in production efficiency by being manufactured by the extrusion method.

Resin sheet WHEREIN: The linear expansion ratio (SR) shown by the relational expression of the linear expansion coefficient (S1) of the layer containing a polycarbonate, and the linear expansion coefficient (S2) of the layer containing a methacrylic resin is in the range of -10% - +5%. From the viewpoint of obtaining good warpage, the linear expansion ratio (SR) is more preferably in the range of -5% to +2%.

The linear expansion ratio (SR) is the ratio (S2 - S1) of the difference (S2 - S1) between the linear expansion coefficient (S1) of the layer containing the polycarbonate and the linear expansion coefficient (S2) of the layer containing the methacrylic resin, and the linear expansion coefficient (S1) ( (S2 - S1)/S1). In other words, in the present specification, the linear expansion ratio (SR) represents the relationship between the linear expansion coefficient (S1) of the polycarbonate-containing layer and the linear expansion coefficient (S2) of the methacrylic resin-containing layer by the formula ((S2 - S1)/S1) make it rain

The lower limit of the glass transition temperature (Tg) of the resin constituting the layer containing the methacrylic resin is usually 120°C, preferably 125°C, more preferably 130°C, and the glass transition temperature (Tg) ) is usually 160°C, preferably 155°C, more preferably 150°C. When the linear expansion ratio (SR) and the glass transition temperature (Tg) of the layer containing the methacrylic resin are within these ranges, the surface properties are good and the warpage resulting from the residual stress is small, which is preferable.

[Methacryl resin]

In one embodiment of the present invention, the methacrylic resin contains a structural unit derived from methacrylic acid ester.

As for content of the structural unit derived from methacrylic acid ester, 50 mass % or more is preferable, More preferably, 80 mass % or more, More preferably, 90 mass % or more is preferable. 100 mass % may be sufficient. When content of the structural unit derived from methacrylic acid ester exists in the above-mentioned range, transparency is favorable.

Such methacrylic acid ester is represented by general formula (IV).

[Formula 4]

In general formula (IV), R represents a hydrocarbon group. A saturated hydrocarbon group may be sufficient as a hydrocarbon group, and an unsaturated hydrocarbon group may be sufficient as it.

The hydrocarbon group represented by R may be an acyclic aliphatic hydrocarbon group such as a methyl group, an ethyl group or a propyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group such as a phenyl group. Here, when R is an alicyclic hydrocarbon group, methacrylic acid ester is represented by general formula (I). Hereinafter, the methacrylic acid ester represented by general formula (I) is appropriately described as "methacrylic acid ester (I)."

[Formula 5]

Examples of methacrylic acid ester (I) include methacrylic acid monocyclic aliphatic hydrocarbon esters such as cyclohexyl methacrylate, cyclopentyl methacrylate, and cycloheptyl methacrylate; 2-norbornyl methacrylate, 2-methyl-2-norbornyl methacrylate, 2-ethyl-2-norbornyl methacrylate, 2-isobornyl methacrylate, 2-methyl-2- Isobornyl methacrylate, 2-ethyl-2-isobornyl methacrylate, 8-tricyclo [5.2.1.0 ^{2, 6} ] decanyl methacrylate, 8-methyl-8-tricyclo [5.2.1.0 ^{2, 6} ] decanyl methacrylate, 8-ethyl-8-tricyclo [5.2.1.0 ^{2, 6} ] decanyl methacrylate, 2-adamantyl methacrylate, 2-methyl-2-adamantyl Methacrylate, 2-ethyl-2-adamantyl methacrylate, 1-adamantyl methacrylate, 2-pentyl methacrylate, 2-methyl-2-pentyl methacrylate or 2-ethyl-2- methacrylic acid polycyclic aliphatic hydrocarbon esters such as pentyl methacrylate; and the like. Especially, methacrylic acid polycyclic aliphatic hydrocarbon ester is preferable, and 8-tricyclo[5.2.1.0 ^{2, 6} ] decanyl methacrylate is more preferable.

It is preferable that the methacrylic resin used in the present invention contains a structural unit derived from methyl methacrylate (hereinafter, appropriately referred to as "MMA") and a structural unit derived from methacrylic acid ester (I), It is more preferable to include a structural unit derived from methyl methacrylate and a structural unit derived from methacrylic acid polycyclic aliphatic hydrocarbon ester, and a structural unit derived from methyl methacrylate and 8-tricyclo[5.2.1.0 ^{2 , 6} ] It is more preferable to include a structural unit derived from decanyl methacrylate.

The methacrylic resin used in the present invention preferably contains 40 to 80 mass% of the structural unit derived from methyl methacrylate from the viewpoint of hardness, more preferably 50 to 80 mass%, When it contains 50-60 mass %, it is more preferable.

The methacrylic resin used in the present invention contains 20 to 60 structural units derived from methacrylic acid ester (I) from the viewpoint of reducing the linear expansion ratio (SR) and making the glass transition temperature (Tg) 120°C or higher. It is preferable to contain by mass %, It is more preferable to contain 20-50 mass %, It is more preferable to contain 40-50 mass %. When the structural unit derived from methacrylic acid ester (I) exceeds 60 mass %, there exists a tendency for the impact resistance of a methacrylic resin layer to fall.

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

As for the weight average molecular weight of the methacryl resin used for this invention (it describes as "Mw" suitably hereafter), 40,000-500,000 are preferable. When such Mw is 40,000 or more, the resin plate of the present invention is excellent in scratch resistance and heat resistance, and when it is 500,000 or less, it is excellent in moldability and productivity of the resin plate of the present invention can be increased.

In addition, in this specification, Mw means the standard polystyrene conversion value measured using gel permeation chromatography (GPC).

In one embodiment of the present invention, the resin constituting the layer containing the methacryl resin is less than 80% by mass of the methacryl resin and at least an aromatic vinyl compound represented by the following general formula (II) (hereinafter, appropriately, “aromatic vinyl compound ( II)") and a copolymer comprising a structural unit derived from an acid anhydride represented by the following general formula (III) .

[Formula 6]

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

[Formula 7]

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

The methacrylic resin contained in the resin composition (1) is a resin containing a structural unit derived from methacrylic acid ester.

Examples of such methacrylic acid esters include methyl methacrylate, 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, and dodecyl methacrylate; methacrylic acid cycloalkyl esters typified by those described as the above-mentioned methacrylic acid ester (I); methacrylic acid aryl esters such as phenyl methacrylate; methacrylic acid aralkyl esters such as benzyl methacrylate; and the like, and from the viewpoint of availability, MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert- methacrylate Butyl is preferred, and MMA is most preferred. 90 mass % or more is preferable, as for content of the structural unit derived from the methacrylic acid ester in a methacrylic resin, 95 mass % or more is more preferable, 98 mass % or more is still more preferable, and it is derived from methacrylic acid ester. It may be only a structural unit that

Further, from the viewpoint of heat resistance, the methacrylic resin contained in the resin composition (1) preferably contains 90 mass% or more of the structural unit derived from MMA, more preferably 95 mass% or more, and 98 mass% or more. % or more is more preferable, and only the structural unit derived from MMA may be sufficient.

In addition, the methacrylic resin contained in the resin composition (1) may contain the structural unit derived from other monomers other than methacrylic acid ester. Examples of such other monomers include methyl acrylate (hereinafter, appropriately referred to as “MA”), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, acrylic acid 2-ethylhexyl, 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, toluyl acrylate, benzyl acrylate, isobornyl acrylate, acrylic acid Acrylic acid esters, such as 3-dimethylaminoethyl, from a viewpoint of availability, Acrylic acid esters, such as MA, ethyl acrylate, acrylate n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate is preferred, MA and ethyl acrylate are more preferred, and MA is most preferred. 10 mass % or less is preferable in total, as for content of the structural unit derived from these other monomers in a methacryl resin, 5 mass % or less is more preferable, and its 2 mass % or less is still more preferable.

The methacrylic resin contained in the resin composition (1) is obtained by superposing|polymerizing the above-mentioned methacrylic acid ester and the other monomer which is an arbitrary component. In such polymerization, when a plurality of types of monomers are used, a monomer mixture is usually prepared by mixing the plurality of types of monomers, and then subjected to polymerization. Although there is no restriction|limiting in particular in the polymerization method, From a viewpoint of productivity, it is preferable to carry out radical polymerization by methods, such as a block polymerization method, a suspension polymerization method, the solution polymerization method, and the emulsion polymerization method.

As for the weight average molecular weight (it describes as "Mw" suitably hereafter) of the methacrylic resin contained in the resin composition (1), 40,000-500,000 are preferable. When this Mw is 40,000 or more, the resin plate of the present invention is excellent in scratch resistance and heat resistance, and when it is 500,000 or less, the resin composition (1) is excellent in moldability and productivity of the resin plate of the present invention can be increased. .

The content of the SMA resin in the resin composition (1) used in the present invention is preferably 20 mass% or more from the viewpoint of reducing the linear expansion ratio (SR) and making the glass transition temperature (Tg) 120 ° C. or more, , more preferably in the range of 45 mass% or more and less than 95 mass%, and still more preferably in the range of 50 mass% or more and less than 90 mass%.

The above-described SMA resin is a copolymer comprising at least a structural unit derived from an aromatic vinyl compound (II) and a structural unit derived from an acid anhydride (III).

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

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

The content of the structural unit derived from the aromatic vinyl compound (II) in the above-mentioned SMA resin is preferably in the range of 50 to 85 mass%, more preferably in the range of 55 to 82 mass%, and in the range of 60 to 80 mass% more preferably. If this content is in the range of 50-85 mass %, the resin composition (1) will be excellent in moisture resistance and transparency.

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

The content of the structural unit derived from the acid anhydride (III) in the above-mentioned SMA resin is preferably in the range of 15 to 50 mass%, more preferably in the range of 18 to 45 mass%, and in the range of 20 to 40 mass%. It is more preferable that When this content exists in the range of 15-50 mass %, the resin composition (1) becomes the thing excellent in heat resistance and transparency.

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

It is preferable that the above-mentioned SMA resin contains the structural unit derived from a methacrylic acid ester monomer in addition to an aromatic vinyl compound (II) and an acid anhydride (III). It is preferable that content of the structural unit derived from the methacrylic acid ester monomer in the above-mentioned SMA resin is in the range of 1-35 mass %, It is more preferable that it is the range of 3-30 mass %, The range of 5-26 mass % It is more preferable that When this content exists in the range of 1-35 mass %, it becomes the thing excellent in bending workability and transparency.

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

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

The above-mentioned SMA resin is obtained by superposing|polymerizing the above-mentioned aromatic vinyl compound (II), acid anhydride (III), and methacrylic acid ester, and the other monomer which is an arbitrary component. In such polymerization, the monomers to be used are usually mixed to prepare a monomer mixture, and then subjected to polymerization. Although there is no restriction|limiting in particular in the polymerization method, From a viewpoint of productivity, it is preferable to carry out radical polymerization by methods, such as a bulk polymerization method and a solution polymerization method.

As for Mw of the above-mentioned SMA resin, the range of 40,000-300,000 is preferable. When such Mw is 40,000 or more, the resin plate of the present invention is excellent in scratch resistance and impact resistance, and when it is 300,000 or less, it is excellent in moldability and productivity of the resin plate of the present invention can be increased.

The resin composition (1) is obtained by mixing the above-mentioned methacrylic resin and SMA resin. Such mixing may use, for example, a melt mixing method, a solution mixing method, or the like. In the melt-mixing method, for example, a melt-kneader such as a single-screw or multi-screw kneader, an open roll, a Banbury mixer, or a kneader is used and, if necessary, melt-kneaded in an inert gas atmosphere such as nitrogen gas, argon gas, or helium gas. carry out In the solution mixing method, methacryl resin and SMA resin are dissolved in organic solvents, such as toluene, tetrahydrofuran, and methyl ethyl ketone, and they are mixed.

Resin which comprises the layer containing the methacryl resin used for one Embodiment of this invention may contain other polymers other than a methacryl resin and SMA resin in the range which does not impair the effect of this invention. Examples of such other polymers include polyolefins such as polyethylene and polypropylene, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyether imide, polyacetal and the like. plastic resin; Thermosetting resins, such as a phenol resin, a melamine resin, a silicone resin, and an epoxy resin; Acrylic rubber, such as multilayer structure particle|grains and a block copolymer, etc. are mentioned. These other polymers may be used individually by 1 type, and may use multiple types together.

The content of these other polymers in the resin constituting the layer containing the methacrylic resin used in one embodiment of the present invention is preferably 10 mass% or less, more preferably 5 mass% or less, and 2 mass% or less more preferably.

When making methacryl resin contain another polymer and/or an additive, when superposing|polymerizing a methacryl resin, you may add, and you may add after superposition|polymerization.

When making resin composition (1) contain another polymer and/or an additive, when superposing|polymerizing a methacryl resin and/or SMA resin, you may add, when mixing a methacryl resin and SMA resin, you may add, and a methacryl resin and SMA resin may be further added after mixing.

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

The resin constituting the layer containing the methacrylic resin used in one embodiment of the present invention preferably has a melt flow rate (hereinafter, appropriately referred to as "MFR") in the range of 1 to 10 g/10 min. , more preferably in the range of 1.5 to 7 g/10 min, and still more preferably in the range of 2 to 4 g/10 min. When the MFR is in the range of 1 to 10 g/10 min, the stability of hot melt molding is good.

In addition, MFR of resin which comprises the layer containing a methacrylic resin in this specification is the value measured under the temperature of 230 degreeC and a 3.8 kg load using a melt indexer.

[Polycarbonate]

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

As the above-mentioned dihydric phenol, 2,2-bis(4-hydroxyphenyl)propane (common name bisphenol A), 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyl) Roxyphenyl)cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyl) phenyl) sulfide, bis (4-hydroxyphenyl) sulfone, etc. are mentioned, Among these, bisphenol A is preferable. These dihydric phenols may be used individually by 1 type, and may use multiple types together.

As above-mentioned carbonate precursor, haloformates, such as carbonyl halides, such as phosgene, carbonate esters, such as diphenyl carbonate, and dihalo formate of dihydric phenol, etc. are mentioned. These carbonate precursors may be used individually by 1 type, and may use multiple types together.

There is no restriction|limiting in particular in the manufacturing method of the above-mentioned polycarbonate, For example, the interfacial polymerization method in which the aqueous solution of a dihydric phenol and the organic solvent solution of a carbonate precursor react at the interface, and a dihydric phenol and a carbonate precursor at high temperature, reduced pressure, and no The transesterification method of reacting under every condition, etc. are mentioned.

The range of 10,000-100,000 is preferable, and, as for Mw of the above-mentioned polycarbonate, it is more preferable that it is the range of 20,000-70,000. When Mw is 10,000 or more, the laminate of the present invention has excellent impact resistance and heat resistance, and when it is 100,000 or less, the polycarbonate is excellent in moldability and productivity of the laminate of the present invention can be increased.

The above-mentioned polycarbonate may contain another polymer in the range which does not impair the effect of this invention. As such another polymer, the thing similar to the other polymer which a methacryl resin, a resin composition (1), and the above-mentioned resin composition (1) may contain can be used. These other polymers may be used individually by 1 type, and may use multiple types together. It is preferable that content of these other polymers in a polycarbonate is 15 mass % or less, It is more preferable that it is 10 mass % or less, It is still more preferable that it is 5 mass % or less.

The above-mentioned polycarbonate may contain various additives as needed. As an additive, the thing similar to the additive which resin which comprises the layer containing the above-mentioned methacrylic resin may contain can be used. Content of these additives can be set suitably in the range which does not impair the effect of this invention, content of antioxidant is 0.01-1 mass parts with respect to 100 mass parts of polycarbonate, content of ultraviolet absorber is 0.01-3 mass parts, As for content of an optical stabilizer, 0.01-3 mass parts is preferable, as for content of 0.01-3 mass parts, a lubricating agent, 0.01-3 mass parts, and content of dye/pigment 0.01-3 mass parts.

When making the above-mentioned polycarbonate contain another polymer and/or an additive, when copolymerizing a dihydric phenol and a carbonate precursor, you may add, after completing such copolymerization, you may add and melt-knead.

It is preferable that it is the range of 120-160 degreeC, as for the glass transition temperature (Tg) of the above-mentioned polycarbonate, it is more preferable that it is the range of 135-155 degreeC, It is still more preferable that it is the range of 140-150 degreeC.

MFR of the above-mentioned polycarbonate is preferably in the range of 1 to 30 g/10 min, more preferably in the range of 3 to 20 g/10 min, still more preferably in the range of 5 to 10 g/10 min. . When the MFR is in the range of 1 to 30 g/10 min, the stability of hot melt molding is good.

In addition, MFR of the polycarbonate in this specification is what measured on the conditions under the temperature of 300 degreeC and 1.2 kg load using a melt indexer.

The above-mentioned polycarbonate may use a commercial item, for example, "Calibur (trademark)" and "SD Polycar (registered trademark)" manufactured by Sumika Styron Polycarbonate Co., Ltd., "Upiron/" manufactured by Mitsubishi Engineering Plastics Co., Ltd. Novarex (registered trademark)”, “Tuplon (registered trademark)” manufactured by Idemitsu Kogsan Co., Ltd., “Fanlite (registered trademark)” manufactured by Teijin Chemicals Co., Ltd., etc. can be preferably used.

[Thickness of resin plate]

The thickness of the resin plate in one Embodiment of this invention becomes like this. Preferably it is 0.1-2 mm, More preferably, it is 0.5-1.5 mm. When it is too thin, there exists a tendency for rigidity to become inadequate. When too thick, there exists a tendency for weight reduction of a liquid crystal display device etc. to become a hindrance.

The thickness of the layer containing the methacrylic resin of the resin plate in one Embodiment of this invention becomes like this. Preferably it is 20-200 micrometers. If it is this range, it is excellent in the balance of abrasion resistance and impact resistance. More preferably, it is 25-150 micrometers, More preferably, it is 30-100 micrometers.

The thickness of the layer containing polycarbonate becomes like this. Preferably it is 0.1-2 mm, More preferably, it is 0.5-1.5 mm. When it is too thin, there exists a tendency for impact resistance to become inadequate. When too thick, there exists a tendency for weight reduction of a liquid crystal display device etc. to become a hindrance.

You may form a cured film on the at least one surface in the resin board obtained by one Embodiment of this invention. By forming a cured film, functions, such as abrasion resistance and low reflection property, can be provided.

For example, the thickness of a scratch-resistant (hard-coat property) cured film becomes like this. Preferably it is 2-30 micrometers, More preferably, it is 5-20 micrometers. When it is too thin, surface hardness will become inadequate, and when it is too thick, a crack may generate|occur|produce by the bending in a manufacturing process.

Moreover, for example, the thickness of a low-reflective cured film becomes like this. Preferably it is 80-200 nm, More preferably, it is 100-150 nm. This is because the low reflection performance becomes insufficient even if it is too thin or too thick.

[Manufacture process]

The resin plate in one embodiment of the present invention is manufactured by co-extrusion. The resin constituting the layer containing the polycarbonate and the methacrylic resin is melted by heating, and a layer containing a methacrylic resin is laminated on at least one side of the layer containing the polycarbonate in the state of a thermoplastic resin laminate, T It is extruded in a molten state from a wide beam-shaped discharge port, called After that, the thermoplastic resin laminate is further wound around a second cooling roll, and then cooled by being wound around a third cooling roll. In addition, the thermoplastic resin laminate (resin plate 16) may be further cooled by further cooling rolls after that.

In FIG. 1, the outline|summary of the manufacturing method of the resin plate by the coextrusion apparatus which consists of the T-die 11, the 1st - 3rd cooling rolls 12-14, and the take-up roll 15 as one Embodiment was shown. The resin extruded from the T-die 11 is sandwiched between a pair of roll furnaces composed of a first cooling roll 12 and a second cooling roll 13 and formed on a sheet-shaped resin plate 16 . Then, the resin plate 16 is further cooled by the 3rd cooling roll 14, and is taken up by the take-up roll 15 which consists of a pair of rolls. You may provide a roll separately between a 3rd cooling roll and a take-up roll. In addition, this invention is not limited to this form.

In this case, the T-die method includes a feed block method in which methacrylic resin and polycarbonate in a heat-melted state are laminated before entering the T-die, and a multi-manifold method in which methacrylic resin and polycarbonate are laminated inside the T die. can be hired From the viewpoint of improving the smoothness of the interface between the layers constituting the resin plate, the multi-manifold system is preferable.

In addition, as a polishing roll in this case, a metal roll or an elastic roll (henceforth a metal elastic roll may be mentioned) etc. which provided the metal thin film in the outer peripheral part are mentioned. It will not specifically limit if it is high rigidity as a metal roll, For example, a drilled roll, a spiral roll, etc. are mentioned. The surface state of a metal roll is not specifically limited, For example, a mirror surface may be sufficient and a pattern, an unevenness|corrugation, etc. may exist. The elastic metal roll includes, for example, a shaft roll formed so as to be able to rotate freely in a substantially circumferential shape, a cylindrical metal thin film disposed so as to cover the outer peripheral surface of the shaft roll and contacting a sheet-like thermoplastic resin, and these shafts; It consists of a fluid enclosed between a roll and a metal thin film, and the metal elastic roll shows elasticity by the fluid. A shaft roll is not specifically limited, For example, it consists of stainless steel etc. It is preferable that the metal thin film consists of stainless steel etc., for example, and the thickness is about 2-5 mm. It is preferable that a metal thin film has flexibility, flexibility, etc., and it is preferable that it is a seamless structure without a weld joint. The metal elastic roll provided with such a metal thin film has excellent durability and can be handled in the same way as a normal mirror roll when the metal thin film is mirror-finished. Because it becomes a roll that can be used, it is convenient to use.

It is preferable to melt-filter the resin and polycarbonate constituting the layer containing the methacrylic resin before and/or at the time of multilayer molding with a filter. By carrying out multilayer molding using each melt-filtered resin composition, a resin plate with few faults resulting from a foreign material and a gel is obtained. There is no limitation in particular in the filter medium of the filter used, It selects suitably by operating temperature, a viscosity, and filtration precision, For example, Nonwoven fabric which consists of polypropylene, cotton, polyester, rayon, glass fiber, etc.; a sheet-like article made of phenol resin-impregnated cellulose; Metal fiber nonwoven fabric sintered sheet-like article; Metal powder sintered sheet-like article; wire mesh ; Or they can be used in combination. Among them, from the viewpoint of heat resistance and durability, it is preferable to laminate and use a plurality of metal fiber nonwoven fabric sintered sheets.

Although there is no restriction|limiting in particular in the filtration precision of the said filter, It is preferable that it is 30 micrometers or less, It is more preferable that it is 10 micrometers or less, It is still more preferable that it is 5 micrometers or less.

In the resin plate according to the embodiment of the present invention, it is preferable that the temperature of the entire resin peeled off from the third cooling roll 14 is in the range of 0°C to +15°C with respect to the glass transition temperature (Tg) of the polycarbonate. . The reason is that when the temperature of the entire resin peeled off from the third cooling roll 14 is lower than the glass transition temperature (Tg) of the polycarbonate, the resin plate transfers the shape of the third cooling roll and the curvature increases. On the other hand, if the temperature of the entire resin peeled off from the third cooling roll 14 is excessively higher than the glass transition temperature (Tg) of the resin layer in contact with the third cooling roll, the resin plate cannot obtain clean surface properties. In addition, the temperature of the whole resin measures and uses the temperature of the whole resin board on which the polycarbonate resin and the methacryl resin were laminated|stacked irrespective of which surface of a resin board.

The resin plate according to one embodiment of the present invention has a linear expansion ratio (SR) in the range of -10% to +5%, and the glass transition temperature (Tg) of the resin layer containing the methacrylic resin is 120 to 160°C. it is preferable The reason is described below.

Since the resin plate peeled from the 3rd cooling roll 14 is pinched|interposed by the 3rd cooling roll 14 and the take-up roll 15, respectively, while it is pinched|interposed by the take-up roll 15, it has a substantially flat shape. . The temperature of the resin plate immediately after being peeled off from the third cooling roll 14 is in the range of 0° C. to +15° C. with respect to the glass transition temperature (Tg) of the polycarbonate, but the temperature of the resin plate near the take-up roll 15 is room temperature. As it cools, it becomes approximately room temperature.

By the way, suppose that the temperature of the resin board peeled from the 3rd cooling roll 14 is 150 degreeC, and the temperature of the resin board near the take-up roll is 25 degreeC, for example. When there is a difference between the coefficient of linear expansion (S1) of the layer containing polycarbonate and the coefficient of linear expansion (S2) of the layer containing the methacrylic resin, specifically, when (S1 - S2)/S1 is other than zero, the coefficient of linear expansion It shrinks to this large side, and warpage occurs.

In addition, for example, the glass transition temperature (Tg) of the layer containing a methacrylic resin shall be 120 degreeC, and let the glass transition temperature (Tg) of the layer containing a polycarbonate be 150 degreeC. In this case, since the temperature of the resin plate peeled from the 3rd cooling roll 14 is 150 degreeC, the layer containing a polycarbonate is cooled to normal temperature from 150 degreeC of glass transition temperature (Tg). Therefore, in the layer containing polycarbonate, it becomes the shrinkage|contraction along the linear expansion coefficient substantially.

On the other hand, the layer containing the methacrylic resin is cooled from a region higher than the glass transition temperature (150°C) to around 120°C of the glass transition temperature (Tg). Therefore, even when there is no difference between the coefficient of linear expansion (S1) of the layer containing polycarbonate and the coefficient of linear expansion (S2) of the resin constituting the layer containing the methacrylic resin, in the layer containing the methacrylic resin, the coefficient of linear expansion is Excessive large shrinkage occurs.

Here, although a general resin is an elastic body below a glass transition temperature, once above a glass transition temperature, it becomes a viscoelastic body which has the function of viscosity and elasticity.

In contrast to the above-mentioned elastic body, which deforms when stress is applied, but is relieved when unloaded, the viscoelastic body undergoes residual strain when cooled to the glass transition temperature with stress applied thereto. When the temperature of the resin plate peeled from the 3rd cooling roll 14 is 150 degreeC, for example, and the layer containing a methacrylic resin and the layer containing a polycarbonate are the above-mentioned glass transition temperatures, a resin plate Immediately after the silver is peeled off from the third cooling roll 14, the polycarbonate layer is an elastic body, whereas the layer containing the methacrylic resin is a viscoelastic body. That is, immediately after peeling the resin plate from the 3rd cooling roll 14, shrinkage deformation will generate|occur|produce only in the layer containing the methacrylic resin which is a viscoelastic body. In other words, since the polycarbonate layer, which is an elastic body, is reversible to stress, it does not deform even under load or unloading of stress. On the other hand, in the layer containing the methacrylic resin which is a viscoelastic body, residual strain generate|occur|produces by the load and unloading of a stress.

From the above, when there is a difference between the coefficient of linear expansion (S1) of the layer containing polycarbonate and the coefficient of linear expansion (S2) of the layer containing methacrylic resin, that is, when the absolute value of the linear expansion ratio (SR) is large, in the elastic body Since warpage occurs due to a difference in the shrinkage of In addition, in order to simplify the explanation up to this point, it may be expressed as a difference in linear expansion. In the case of describing simple largeness and smallness, it can be sufficiently expressed by difference, but in the case of expressing quantitative warpage, it is necessary to discuss with the linear expansion ratio (SR).

Further, the glass transition temperature (Tg) of the layer containing the methacrylic resin is lower than the glass transition temperature (Tg) of the layer containing the polycarbonate, and the temperature of the resin plate peeled from the third cooling roll 14 is When it is between the glass transition temperature (Tg) of the layer containing the methacrylic resin and the glass transition temperature (Tg) of the layer containing the polycarbonate, the methacrylic resin is contained by the difference in shrinkage between the elastic body and the viscoelastic body. The strain remains in the layer. This residual strain tends to open up strain by exposure to high temperature and high temperature, high humidity conditions, and warpage occurs. Here, since the temperature of the resin plate immediately after peeling from the 3rd cooling roll 14 is 0 degreeC - +15 degreeC with respect to the glass transition temperature (Tg) of polycarbonate, the state of a viscoelastic body also exists in polycarbonate. Here, although the temperature of the resin plate is cooled to normal temperature up to the take-up roll 15, the layer containing a methacrylic resin and the layer containing a polycarbonate are simultaneously cooled to normal temperature. Therefore, the temperature of the resin plate from immediately after peeling from the third cooling roll 14 to the take-up roll 15 is the glass transition temperature (Tg) of the polycarbonate and the glass transition temperature of the layer containing the methacrylic resin ( Tg) will be included. In other words, while the temperature of the resin plate is cooled from the glass transition temperature (Tg) of the polycarbonate to the glass transition temperature (Tg) of the layer containing the methacrylic resin, deformation remains in the layer containing the methacrylic resin.

On the other hand, in principle, when the temperature of the resin plate peeled from the third cooling roll 14 is lower than 150°C, the curvature and residual stress due to the linear expansion ratio SR tend to decrease, so the curvature becomes small. However, as mentioned above, the curvature which arises when a resin plate transcribe|transfers the shape of the 3rd cooling roll 14 becomes large, and it is unpreferable.

In this regard, in order to achieve the object of the present application, the temperature of the resin peeled off from the third cooling roll 14 is in the range of 0°C to +15°C with respect to the glass transition temperature (Tg) of the polycarbonate, and the linear expansion ratio (SR ) is in the range of -10% to +5%, and the glass transition temperature (Tg) of the layer containing the methacrylic resin is 120 to 160°C, so that it has been found that a good resin plate with small curvature is obtained.

Example

Hereinafter, an Example is shown and this invention is demonstrated in more detail. However, the present invention is not limited by these examples at all.

The physical properties of the resin plate were measured by the following method.

[Glass Transition Temperature (Tg)]

After the obtained resin plate was dried under reduced pressure (1 kPa) at 80° C. for 24 hours, a 10 mg test piece was cut out, sealed in an aluminum pan, and a differential scanning calorimeter (“DSC-50”, manufactured by Rigaku Co., Ltd.) was used. Thus, nitrogen substitution was performed for 30 minutes or longer. Thereafter, in a nitrogen stream of 10 ml/min, the temperature was once raised from 25°C to 200°C at a rate of 20°C/min, held for 10 minutes, and cooled to 25°C (first injection). Then, it heated up to 200 degreeC at the rate of 10 degreeC/min (2nd scan), and computed the glass transition temperature (Tg) by the midpoint method.

[Linear expansion rate]

The coefficient of linear expansion is defined as the rate of change in length per unit temperature change. The coefficient of linear expansion was measured according to JIS K7197 using a thermomechanical analyzer ("TMA4000" manufactured by Bruker AXS Co., Ltd.). That is, the sheet-shaped resin plate obtained by press-molding the resin to be measured was processed into a prismatic shape with a side length of 5 mm × 5 mm and a height of 10 mm using diamond saw to form a smooth cross section, Each sample was placed on a quartz plate with a surface of 5 mm x 5 mm in contact with the quartz plate, a cylindrical rod was placed thereon, and a compressive load of 5 g was applied to fix it. Then, the temperature was raised from 25°C (room temperature) to minus 10°C of the glass transition temperature (Tg) of each sample in an air atmosphere at a temperature increase rate of 3°C/min, and cooled to 25°C (room temperature) (first injection). And it heated up from 25 degreeC (room temperature) to +20 degreeC of the glass transition temperature (Tg) of each sample at a temperature increase rate of 3 degree-C/min (2nd scan). The expansion coefficient at each temperature at the time of secondary scanning was measured, and the average linear expansion coefficient in the range of 30 degreeC - 80 degreeC was calculated|required.

[Deflection amount]

The resin plates of Examples and Comparative Examples were cut into a rectangle such that a direction parallel to the extrusion flow direction became a short side and a direction perpendicular to the extrusion flow direction became a long side, and a test piece having a short side of 65 mm and a long side of 110 mm was prepared. The produced test piece was set so that the layer containing a methacrylic resin might become upward on a surface plate, and it was left to stand in the environment of the temperature of 23 degreeC, and 50% of a relative humidity for 24 hours. Thereafter, the maximum value of the gap between the test piece and the surface plate was measured using a gap gauge, and this value was taken as the initial warpage amount. Next, the test piece is placed in an environmental tester set to a temperature of 85°C and a relative humidity of 85% so that the layer containing the methacrylic resin is facing upward on a glass platen, and then left in that state for 72 hours, and then in an environment of 25°C It was left for 4 hours. Then, it measured similarly to the above, and made this value into the amount of curvature after high temperature, high humidity. The test piece was put on a surface plate so that the layer containing a methacrylic resin turned upward, the sign of downward convex bending was made into plus, and the sign of upward convex bending was made into minus. As for the amount of deflection, ±0.5 mm or less was considered a pass.

[Surface property]

In a room equipped with a fluorescent lamp, both surfaces of the resin plate were visually observed, and the surface properties were evaluated according to the following criteria.

(circle): A chatter mark is not seen on the resin board surface.

△: Chatter marks are visible on the surface of the resin plate, but are not conspicuous

x: A chatter mark stands out on the resin board surface.

[resin temperature]

The temperature of the whole resin plate 16 at the position where it peels from the 3rd cooling roll 14 was measured with the infrared radiation thermometer. The temperature measured in this way shall be called resin temperature (TT).

[Methacrylic resin A]

"Parapet (registered trademark) HR" manufactured by Kuraray Co., Ltd. (MFR at a temperature of 230°C and a load of 3.8 kg = 2.4 g/10 min) was prepared as the methacrylic resin A.

[methacrylic resin B]

A copolymer obtained by radical polymerization of methyl methacrylate and 8-tricyclo[5.2.1.0 ^{2, 6} ] decanyl methacrylate was prepared as methacrylic resin B.

In addition, the injection ratio of 8-tricyclo[5.2.1.0 ² , 6 ] decanyl methacrylate to the total amount of methyl methacrylate and 8-tricyclo [5.2.1.0 ^{2, 6} ] decanyl methacrylate ( mass percentage) is referred to as the TC ratio.

[methacrylic resin C]

From the center side, 35 mass % of hard layer (1st layer: 94 mass parts of MMA units, 6 mass parts of methyl acrylate units, 0.2 mass parts of allyl methacrylate units), 45 mass % of soft layers (2nd layer, rubber layer: acrylic acid) 82.2 parts by mass of butyl unit, 17.8 parts by mass of styrene unit, 2 parts by mass of allyl methacrylate unit), and 20 mass% of hard layer (third layer: 94 parts by mass of MMA unit, 6 parts by mass of methyl acrylate unit, n-octylmer) Captan unit 0.2 parts by mass) and having an average particle diameter of 0.23 m, acrylic 3-layer structure rubber particles were prepared.

The resin composition which mixed 8.5 mass % of 91.5 mass % of methacryl resin B with a TC ratio of 35 mass %, and the said average particle diameter of 0.23 micrometer acrylic 3-layer structure rubber particle was prepared as methacryl resin C.

[Resin Composition (1)]

In the manufacture example, the methacrylic resin and SMA resin shown below were used.

<Methacrylic resin>

The methacryl resin prepared the above-mentioned "Parapet (trademark) HR" by Kuraray Co., Ltd. (the same as the methacryl resin A) as a methacryl resin.

<SMA resin>

SMA resin can be obtained by the following method.

For example, by the method described in WO2010/013557, an SMA resin which is a styrene-maleic anhydride-MMA copolymer can be obtained.

Table 1 shows the mass composition ratio and weight average molecular weight (Mw) of the used SMA resin.

<Mass composition ratio>

The copolymer composition of the SMA resin was determined by 13 C-NMR method in the following procedure.

For the 13 C-NMR spectrum, a nuclear magnetic resonance apparatus (GX-270 manufactured by Nippon Electronics Co., Ltd.) was used. 1.5 g of SMA resin was melt|dissolved in 1.5 ml of deuterated chloroform, the sample solution was adjusted, and it measured under the conditions of 4000-5000 times of integration times in a room temperature environment. From the measurement result, the following values were calculated|required.

- [Integrated intensity of the carbon peak (near 127, 134, 143 ppm) of the benzene ring (carbon number 6) in the styrene unit]/6

- [Integrated intensity of the carbon peak (near 170 ppm) of the carbonyl moiety (carbon number 2) in the maleic anhydride unit]/2

- [Integrated intensity of the carbon peak (near 175 ppm) of the carbonyl moiety (carbon number of 1) in the MMA unit]/1

The molar ratio of the styrene unit, the maleic anhydride unit, and the MMA unit in a sample was calculated|required from the area ratio of the above values. The mass composition of each monomer in SMA resin was calculated|required from the obtained molar ratio and the mass ratio of each monomer unit (styrene unit: maleic anhydride unit: MMA=104:98:100).

<Weight Average Molecular Weight (Mw)>

Mw of SMA resin was calculated|required by the GPC method in the following procedure.

Tetrahydrofuran was used as an eluent, and what connected two of TSKgel SuperMultipore HZM-M by Tosoh Corporation and SuperHZ4000 in series as a column was used. As the GPC apparatus, HLC-8320 (product number) manufactured by Tosoh Corporation equipped with a differential refractive index detector (RI detector) was used. A sample solution was prepared by dissolving 4 mg of SMA resin in 5 ml of tetrahydrofuran. The temperature of the column oven was set to 40 degreeC, and 20 microliters of sample solutions were inject|poured with the eluent flow volume 0.35 ml/min, and the chromatogram was measured. The molecular weight measured 10 standard polystyrene points in the range of 400 to 5000000 by GPC, and created a calibration curve showing the relationship between the holding time and the molecular weight. Based on this calibration curve, Mw was determined.

The injection ratio (mass percentage) which the SMA resin in the resin composition (1) occupies in the total amount of the methacrylic resin A and SMA resin shall be called SMA ratio.

[Polycarbonate]

"SD Polycar (registered trademark) PCX" manufactured by Sumika Styron Polycarbonate Co., Ltd. (Temperature 300 ° C, MFR under 1.2 kg load = 6.7 g/10 min, glass transition temperature (Tg) = 150 ° C., coefficient of linear expansion = 6.93 × 10 ^-5 /K) was prepared as polycarbonate.

[Example 1]

(Method for producing a resin plate)

Methacrylic resin B (glass transition temperature: 120 degrees, coefficient of linear expansion: 7.30 x 10 ^-5 /K) having a TC ratio of 20 mass% was used with a 150 mmφ single screw extruder [manufactured by Toshiba Machinery Co., Ltd.], and polycarbonate was subjected to 150 mmφ Each was melted with a single screw extruder (manufactured by Toshiba Machinery Co., Ltd.), and both were laminated through a multi-manifold die. The laminated resin (resin plate 16, thermoplastic resin laminate in a molten state) is sandwiched between a first cooling roll 12 and a second cooling roll 13 as shown in FIG. 1, and a second cooling roll 13 ), it was cooled by winding around the 3rd cooling roll 14, and the resin plate 16 was taken up with the take-up roll 15 and manufactured. Resin temperature TT was adjusted to 150 degreeC by controlling the temperature of the 2nd cooling roll 13 and the 3rd cooling roll 14. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Example 2]

The resin plate was manufactured using the methacryl resin B and polycarbonate of 35 mass % of TC ratios similarly to the above-mentioned. Resin temperature (TT) was adjusted to 150 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Example 3]

Methacrylic resin B and polycarbonate with a TC ratio of 45 mass % were manufactured similarly to the above-mentioned. Resin temperature (TT) was adjusted to 155 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Example 4]

Methacrylic resin B and polycarbonate having a TC ratio of 60% by mass were produced in the same manner as described above. Resin temperature (TT) was adjusted to 155 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Example 5]

The resin composition (1) and polycarbonate of 20 mass % of SMA ratio were manufactured similarly to the above-mentioned. Resin temperature (TT) was adjusted to 150 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Example 6]

The resin composition (1) and polycarbonate of 50 mass % of SMA ratio were manufactured similarly to the above-mentioned. Resin temperature (TT) was adjusted to 150 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Example 7]

The resin composition (1) and polycarbonate with an SMA ratio of 70 mass % were manufactured similarly to the above-mentioned. Resin temperature (TT) was adjusted to 155 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Example 8]

The resin composition (1) and polycarbonate of 100 mass % of SMA ratio were manufactured similarly to the above-mentioned. Resin temperature (TT) was adjusted to 155 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Example 9]

The resin composition (1) and polycarbonate with an SMA ratio of 70 mass % were manufactured similarly to the above-mentioned. Resin temperature (TT) was adjusted to 165 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Comparative Example 1]

Methacrylic resin A and polycarbonate were prepared in the same manner as described above. Resin temperature (TT) was adjusted to 150 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Comparative Example 2]

The resin composition (1) and polycarbonate with an SMA ratio of 70 mass % were manufactured similarly to the above-mentioned. Resin temperature (TT) was adjusted to 145 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Comparative Example 3]

The resin composition (1) and polycarbonate with an SMA ratio of 70 mass % were manufactured similarly to the above-mentioned. Resin temperature (TT) was adjusted to 170 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

[Comparative Example 4]

Except having changed the methacryl resin B of 35 mass % of TC ratios into the methacryl resin C, it carried out similarly to Example 2, and produced the resin plate. Resin temperature (TT) was adjusted to 150 degreeC similarly to the above-mentioned. Table 2 shows the manufacturing conditions and the evaluation result of the obtained resin plate.

In Table 2, for each of Examples and Comparative Examples, the resin temperature (TT), the glass transition temperature (Tg), the coefficient of linear expansion of the resin plate, the linear expansion ratio (SR), the amount of warpage after the initial stage and high temperature and humidity, and the measurement of surface properties shows the results.

In Examples 1-4, the resin board which laminated|stacked the layer containing the methacrylic resin B of 20-60 mass % of TC ratio, and the layer containing polycarbonate was manufactured and tested. As shown in Table 2, when using the layer containing the methacrylic resin B with a TC ratio of 45% of Example 3, considering the glass transition temperature (Tg), the linear expansion ratio (SR), and the amount of warp, it is the most This was a desirable result.

In Examples 5 to 9, a resin plate in which a layer containing the resin composition (1) having an SMA ratio of 20 to 100 mass% and a layer containing polycarbonate were laminated was produced and tested. As shown in Table 2, when using the layer containing the resin composition (1) of 70 mass % of SMA ratios of Examples 7 and 9, the absolute value of curvature amount was small, and it became the most preferable result.

On the other hand, in the comparative example 1, the glass transition temperature (Tg) was low and the curvature after high temperature, high humidity was large. In the comparative example 2, as a result of making resin temperature (TT) low, it became a resin plate with a large amount of curvature. In the comparative example 3, as a result of making resin temperature (TT) high, it became a resin board with bad surface property. In Comparative Example 4, since the requirement of the coefficient of linear expansion did not satisfy the present application, the initial warpage and warpage after high temperature and high humidity were large.

Industrial Applicability

The resin plate of this invention can be used for the protective cover of a liquid crystal display protective plate and a touch panel, for example, and is suitable for an in-vehicle display device, a mobile phone, a smart phone, a PC, a television, etc.

In addition, this invention is not limited to the above-mentioned embodiment, It is possible to change suitably in the range which does not deviate from the meaning.

This application claims priority on the basis of Japanese Patent Application No. 2014-190029 for which it applied on September 18, 2014, and uses all the indications here.

11 T die
12 first cooling roll
13 Second Cooling Roll
14 third cooling roll
15 take-up rolls
16 resin board

Claims (7)

A method for producing an extruded resin plate in which a layer containing a methacrylic resin is laminated on at least one side of a layer containing polycarbonate,
The layer containing the methacrylic resin is less than 80% by mass of the methacrylic resin, and at least a structural unit derived from an aromatic vinyl compound represented by the following general formula (II) and an acid anhydride represented by the following general formula (III). It contains 20 mass% or more of the copolymer consisting of structural units,
The difference (S2 - S1) between the coefficient of linear expansion (S1) of the layer containing the polycarbonate and the coefficient of linear expansion (S2) of the layer containing the methacrylic resin, and the coefficient of linear expansion of the layer containing the polycarbonate (S1) ratio ((S2 - S1)/S1) of -10% to +5%,
The glass transition temperature of the layer containing the said methacrylic resin shall be 120-160 degreeC,
Extruding the thermoplastic resin laminate in which the layer containing the methacrylic resin is laminated on at least one side of the layer containing the polycarbonate in a molten state from a T-die,
sandwiching the thermoplastic resin laminate between the first cooling roll and the second cooling roll;
After the thermoplastic resin laminate is wound around the second cooling roll, it is cooled by winding it around a third cooling roll,
a step of taking the thermoplastic resin laminate with a take-up roll;
In the position where the thermoplastic resin laminate is peeled off from the third cooling roll, the temperature of the entire resin is in the range of 0 ° C. to +15 ° C. with respect to the glass transition temperature of the polycarbonate-containing layer. manufacturing method.
[Formula 2]

(In the formula: R ¹ and R ² each independently represent a hydrogen atom or an alkyl group.)
[Formula 3]

(In the formula: R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group.) The method of claim 1,
The said copolymer contains 50-84 mass % of the structural unit derived from the said aromatic vinyl compound, contains 15-49 mass % of the structural unit derived from the said acid anhydride, 1-25 mass % of a methacrylic acid ester monomer The manufacturing method of the extruded resin board characterized by containing. 3. The method of claim 2,
The method for producing an extruded resin plate, characterized in that the methacrylic acid ester monomer is methyl methacrylate. The process of manufacturing an extruded resin board by the manufacturing method of the extruded resin board in any one of Claims 1-3;
The manufacturing method of the extruded resin board with an abrasion-resistant layer which has the process of forming an abrasion-resistant layer in at least one surface of the said extruded resin board. delete delete delete

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