CN105899360A - Thermoplastic resin laminate - Google Patents

Abstract

According to the present invention, it is possible to provide a thermoplastic resin laminate comprising a layer (A) comprising a thermoplastic resin composition and a layer (B) comprising an acrylic resin composition provided on at least one surface of the layer (A) , the above-mentioned thermoplastic resin composition contains polyester resin (a) and polycarbonate resin (b), and this polyester resin (a) contains dibasic alcohol structural unit and dicarboxylic acid structural unit, wherein, all dibasic alcohol structural unit 10 to 60 mol% of the diol structural unit derived from the diol having a cyclic acetal skeleton represented by the above formula (1) or formula (2), relative to the polyol in the above thermoplastic resin composition The total of the ester resin (a) and the polycarbonate resin (b), the proportion of the polycarbonate resin (b) is 5 to 50% by weight, and the above-mentioned acrylic resin composition contains At least one of the methyl ester-styrene copolymers (d) and the styrene-maleic anhydride copolymer (e).

Description

thermoplastic resin laminate

technical field

The present invention relates to a thermoplastic resin laminate, in particular to a thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high-temperature, high-humidity environment.

Background technique

Resin-made transparent boards are widely used in exterior applications such as outdoor signboards and carports, and optical applications in OA equipment and display front panels of portable electronic equipment. In recent years, in front panels of portable display devices such as mobile phone terminals, portable video game machines, and portable information terminals, not only transparency, visibility, and scratch resistance, but also high dimensional stability. As a transparent resin used for such a front panel, an acrylic resin excellent in transparency, weather resistance, and scratch resistance is widely used. However, acrylic resins lack impact resistance, and there is a problem that the front panel is likely to be cracked in applications where impacts are easily applied, such as touch panel displays.

In Patent Document 1, it is described that a diol unit having a cyclic acetal skeleton represented by general formula (1) or general formula (2) is contained in 10 to 60 mol% of the diol structural unit, or the diol unit is represented by 10 to 60 mol% of the dicarboxylic acid structural unit contains a polyester resin (a) having a dicarboxylic acid unit having a cyclic acetal skeleton represented by general formula (3) or general formula (4) as a center layer and A structure using an acrylic resin for the surface layer provides a multilayer sheet excellent in transparency, heat resistance, scratch resistance, and impact resistance.

(In formulas (1) and (2), R ¹ , R ² and R ³ are independently selected from aliphatic groups with 1 to 10 carbon atoms, alicyclic groups with 3 to 10 carbon atoms Groups and organic groups in aromatic groups with 6 to 10 carbon atoms.)

(In formulas (3), (4), R ⁴ and R ⁵ are independently independent, representing an aliphatic group with 1 to 10 carbon atoms, an alicyclic group with 3 to 10 carbon atoms, and a carbon An organic group in an aromatic group with 6 to 10 atoms, R ⁶ and R ⁷ are each independently representing a hydrogen atom, a methyl group, an ethyl group or an isopropyl group.)

However, although the multilayer sheet disclosed in this gazette has excellent heat resistance in a low-humidity environment, it does not have sufficient dimensional stability in a high-temperature, high-humidity environment such as a temperature of 85° C. and a humidity of 85%.

prior art literature

patent documents

Patent Document 1: Japanese Unexamined Patent Publication No. 2003-182014

Contents of the invention

The problem to be solved by the invention

The object of the present invention is to solve at least one of the above conventional problems. Another object of the present invention is to provide a thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high-temperature, high-humidity environment.

method used to solve the problem

As a result of intensive studies, the inventors of the present invention have found that the above-mentioned problems can be solved by the following present invention.

That is, the present invention is as follows.

<1> A thermoplastic resin laminate, characterized in that:

having a layer (A) containing a thermoplastic resin composition and a layer (B) provided on at least one surface of the layer (A) and containing an acrylic resin composition,

Above-mentioned thermoplastic resin composition contains polyester resin (a) and polycarbonate resin (b), and this polyester resin (a) contains dibasic alcohol structural unit and dicarboxylic acid structural unit, wherein, in all dibasic alcohol structural units 10 to 60 mol% of the dihydric alcohol structural unit derived from the dihydric alcohol having a cyclic acetal skeleton represented by the following formula (1) or the following formula (2), relative to the poly The total of the ester resin (a) and the polycarbonate resin (b), the ratio of the polycarbonate resin (b) is 5 to 50% by weight,

(In formulas (1) and (2), R ¹ , R ² and R ³ are independently selected from aliphatic groups with 1 to 10 carbon atoms, alicyclic groups with 3 to 10 carbon atoms Groups and organic groups in aromatic groups with 6 to 10 carbon atoms.)

The above-mentioned acrylic resin composition contains at least one selected from the group consisting of acrylic resin (c) and methyl methacrylate-styrene copolymer (d) and styrene-maleic anhydride copolymer (e), relative to the above-mentioned acrylic acid The total of the structural units derived from methyl methacrylate, the structural units derived from styrene, and the structural units derived from maleic anhydride in the resin-like composition, the ratio of the structural units derived from methyl methacrylate is 70 to 95 mol % , the ratio of the structural unit derived from maleic anhydride is 1 to 5 mol%.

<2> The thermoplastic resin laminate as described in the above <1>, wherein the total of structural units derived from styrene and structural units derived from maleic anhydride in the styrene-maleic anhydride copolymer (e) is , The proportion of structural units derived from styrene is 75 to 95% by weight.

<3> The thermoplastic resin laminate according to the above <1> or <2>, wherein the diol having a cyclic acetal skeleton is 3,9-bis(1,1-dimethyl- 2-Hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

<4> The thermoplastic resin laminate according to any one of the above <1> to <3>, wherein, in the polyester resin (a), all dicarboxylic acid structural units are derived from terephthalic acid The ratio of the structural unit is 70 mol% or more.

<5> The thermoplastic resin laminate according to any one of <1> to <4>, wherein one or both surfaces are subjected to a hard coat treatment.

<6> The thermoplastic resin laminate according to any one of the above <1> to <5>, wherein one or both surfaces are treated with antireflection treatment, antifouling treatment, antistatic treatment, Any one or more of weather resistance treatment and anti-stun treatment.

<7> A transparent substrate material comprising the thermoplastic resin laminate according to any one of <1> to <6>.

<8> A transparent protective material comprising the thermoplastic resin laminate according to any one of the above <1> to <6>.

The effect of the invention

According to a preferred aspect of the present invention, it is possible to provide a thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high-temperature, high-humidity environment, and the thermoplastic resin laminate can be used as It is suitable for use as a transparent substrate material, a transparency protective material, etc., and is especially suitable for front panels and the like of portable display devices that require high dimensional stability in high-temperature and high-humidity environments.

detailed description

The present invention will be described in detail below. The thermoplastic resin laminate of the present invention is characterized by having a layer (A) containing a thermoplastic resin composition and a layer (B) containing an acrylic resin composition, and having the layer (A) on at least one surface of the layer (A). B), the above-mentioned thermoplastic resin composition comprises polyester resin (a) and polycarbonate resin (b), and in the diol structural unit of above-mentioned polyester resin (a), contains the diol derived from having cyclic acetal skeleton The glycol structural unit of the alcohol, the above-mentioned acrylic resin composition contains at least one selected from the group consisting of acrylic resin (c) and methyl methacrylate-styrene copolymer (d) and styrene-maleic anhydride copolymer thing (e).

The polyester resin (a) used in the present invention contains 10 to 60 mole % of all diol structural units derived from the cyclic acetal skeleton represented by the following formula (1) or the following formula (2). The diol structure unit of the diol and the polyester resin of the dicarboxylic acid structure unit.

(In formulas (1) and (2), R ¹ , R ² and R ³ are independently selected from aliphatic groups with 1 to 10 carbon atoms, alicyclic groups with 3 to 10 carbon atoms Groups and organic groups in aromatic groups with 6 to 10 carbon atoms.)

Among the dihydric alcohols having a cyclic acetal skeleton represented by the above formula (1) or formula (2), R ¹ and R ² are preferably methylene, ethylene, propylene, butylene or their Isomers, for example, isopropylene, isobutylene, and the like. R ³ preferably represents methyl, ethyl, propyl, butyl or their isomers, such as isopropyl, isobutyl and the like. Among them, as the diol having a cyclic acetal skeleton, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxa spiro[5.5]undecane, 5-hydroxymethyl-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane, particularly preferably 3,9 - Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

The diol structural unit other than the diol structural unit derived from diol having a cyclic acetal skeleton in the polyester resin (a) used in the present invention is not particularly limited, and ethylene glycol, Aliphatic diols such as trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene glycol, neopentyl glycol, etc.; polyethylene Polyether compounds such as diol, polypropylene glycol, and polytetramethylene glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decalindimethanol, 1,3 - Decalin dimethanol, 1,4-decalin dimethanol, 1,5-decalin dimethanol, 1,6-decalin dimethanol, 2,7-decalin dimethanol, tetralin Alicyclic diols such as dimethanol, norbornene dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol, etc.; 4,4'-(1-methylethylene) bisphenol, methyl bisphenols such as bisphenol (bisphenol F), 4,4'-cyclohexylene bisphenol (bisphenol Z), 4,4'-sulfonyl diphenol (bisphenol S); Alkylene oxide adducts; hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyldiphenyl An aromatic dihydroxy compound such as benzophenone; and a diol structural unit derived from an alkylene oxide adduct of the above-mentioned aromatic dihydroxy compound. As diol structural units other than diol structural units derived from diols having a cyclic acetal skeleton, among these, structural units derived from ethylene glycol are particularly preferred.

The dicarboxylic acid structural unit of the polyester resin (a) used in the present invention is not particularly limited, and can be exemplified from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid. , sebacic acid, dodecane dicarboxylic acid, cyclohexane dicarboxylic acid, decane dicarboxylic acid, norbornene dicarboxylic acid, tricyclodecane dicarboxylic acid, pentacyclododecane dicarboxylic acid, etc. Aliphatic dicarboxylic acids and their ester-forming derivatives; terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, tetra Dicarboxylic acid structural units of aromatic dicarboxylic acids such as hydrogenated naphthalene dicarboxylic acid and ester-forming derivatives thereof. Among these, dicarboxylic acid structural units derived from terephthalic acid and 3-naphthalene dicarboxylic acid are more preferred, and terephthalic acid is particularly preferred.

In the polyester resin (a) used in the present invention, the ratio of diol structural units derived from diols having a cyclic acetal skeleton in all diol structural units is preferably 10 to 60 mol%, More preferably, it is 15 to 50 mol%. When the said ratio is less than 10 mol%, since polyester resin (a) may not express sufficient heat resistance, it is unpreferable. Moreover, since impact resistance may fall when it exceeds 60 mol%, it is unpreferable.

In the polyester resin (a), the proportion of terephthalic acid-derived structural units in all dicarboxylic acid structural units is preferably 70 mol % to 100 mol %, more preferably 90 mol % to 100 mol %. When the polyester resin (a) has the above-mentioned diol structural unit and dicarboxylic acid structural unit, the thermoplastic resin laminate of the present invention is more excellent in heat resistance, mechanical properties and economic efficiency.

The method for producing the polyester resin (a) used in the present invention is not particularly limited, and conventionally known methods can be applied. For example, melt polymerization methods such as transesterification methods and direct esterification methods, solution polymerization methods, and the like can be mentioned. To the polyester resin (a), various additives commonly used may be added, and examples of additives include various stabilizers such as transesterification catalysts, esterification catalysts, ether inhibitors, heat stabilizers, and light stabilizers. , polymerization regulator, etc.

The polycarbonate resin (b) used in the present invention is obtained by interfacial polymerization of an aromatic dihydroxy compound or a small amount of polyhydroxy compound and phosgene, or the above-mentioned aromatic dihydroxy compound and carbonic acid A thermoplastic polycarbonate polymer that may have branched chains produced by a diester by transesterification, for example, a carbonate polymer that uses bisphenol A as a main raw material. The molecular weight of the polycarbonate resin (b) to be used is preferably a molecular weight capable of producing a sheet by normal extrusion molding, and the weight average molecular weight is preferably 45,000 to 70,000 in terms of polystyrene. Within the range of this weight average molecular weight, the polycarbonate resin base material has a coefficient of linear expansion in the range of 6×10 ^-5 /°C to 8×10 ^-5 /°C. To the polycarbonate resin (b), various additives commonly used may also be added. Examples of additives include antioxidants, anti-coloring agents, ultraviolet absorbers, light diffusing agents, flame retardants, mold release agents, lubricating agents, and Agents, antistatic agents, dyes, etc.

As the ratio of the polyester resin (a) and the polycarbonate resin (b) in the above-mentioned thermoplastic resin composition, with respect to the total of the polyester resin (a) and the polycarbonate resin (b), the polycarbonate resin (b) ) is preferably 5 to 50% by weight. When the polycarbonate resin (b) is less than 5% by weight, the dimensional stability in a high-temperature, high-humidity environment deteriorates, and when it exceeds 50% by weight, the Tg of the thermoplastic resin composition becomes high, which is different from that of an acrylic resin composition. The difference in Tg between the layers (B) becomes large, making it difficult to form a flat molded product. By setting the ratio of the polyester resin (a) and the polycarbonate resin (b) in the thermoplastic resin composition within the above-mentioned range, the thermoplastic resin laminate of the present invention can obtain impact resistance and dimensional stability in a high-temperature, high-humidity environment. Such an advantage of excellent performance. The proportion of the polycarbonate resin (b) is more preferably in the range of 10 to 50% by weight, more preferably in the range of 20 to 50% by weight, based on the total of the polyester resin (a) and the polycarbonate resin (b).

The above-mentioned thermoplastic resin composition may contain resins other than the polyester resin (a) and the polycarbonate resin (b). As resins other than polyester resin (a) and polycarbonate resin (b), for example, polyethylene terephthalate, polyethylene naphthalate, isophthalic acid-modified polyethylene terephthalate, Polyester resins other than the polyester resin (a) such as ethylene phthalate, 1,4-cyclohexanedimethanol-modified polyethylene terephthalate, and polyarylate.

The acrylic resin (c) used in the present invention contains a methyl methacrylate polymer. The weight average molecular weight of the acrylic resin (c) is preferably 10,000 to 30,000 in terms of polystyrene.

The methyl methacrylate-styrene copolymer (d) used in the present invention contains 5 to 99% by weight of structural units derived from methyl methacrylate and 95 to 1% by weight of structural units derived from styrene. copolymer. It is preferably a copolymer comprising 50 to 95% by weight of structural units derived from methyl methacrylate and 50 to 5% by weight of structural units derived from styrene, more preferably 60 to 90% by weight of structural units derived from methyl methacrylate A copolymer of ester structural units and 40 to 10% by weight of styrene-derived structural units. When the structural unit derived from methyl methacrylate is less than 5% by weight and the structural unit derived from styrene exceeds 95% by weight, transparency decreases and the appearance deteriorates. The weight average molecular weight of the methyl methacrylate-styrene copolymer (d) is preferably 10,000 to 30,000 in terms of polystyrene.

It is preferable to use an acrylic resin (c) and/or a methyl methacrylate-styrene copolymer ( d), the thermoplastic resin laminate of the present invention can obtain the advantages of being excellent in transparency and scratch resistance.

The styrene-maleic anhydride copolymer (e) used in the present invention is a copolymer containing 75 to 95% by weight of structural units derived from styrene and 25 to 5% by weight of maleic anhydride. It is preferably a copolymer comprising 78 to 92% by weight of structural units derived from styrene and 22 to 8% by weight of maleic anhydride, more preferably comprising 80 to 90% by weight of structural units derived from styrene and 20 to 10% by weight % of maleic anhydride copolymers. The weight average molecular weight of the styrene-maleic anhydride copolymer (e) is preferably 10,000 to 30,000 in terms of polystyrene. When the structural unit derived from styrene is less than 75% by weight and maleic anhydride exceeds 25% by weight, the transparency may decrease and the appearance may deteriorate. Also, when the structural unit derived from styrene exceeds 95% by weight and the maleic anhydride is less than 5% by weight, the transparency decreases, and the effect of improving heat resistance and hygroscopicity is small. By having the above-mentioned composition, the thermoplastic resin laminate of the present invention can obtain an advantage of being excellent in dimensional stability in a high-temperature, high-humidity environment.

The above-mentioned acrylic resin composition may contain other resin components other than the acrylic resin (c), methyl methacrylate-styrene copolymer (d), and styrene-maleic anhydride copolymer (e). Examples of other resin components include polyesters other than the polyester resin (a), polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymers, methyl methacrylate-methacrylic acid copolymers , methyl methacrylate-acrylic acid copolymer, methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-methacrylonitrile copolymer, methyl methacrylate and N-phenylmaleimide Copolymer of methyl methacrylate and N-cyclohexylmaleimide, styrene-methyl methacrylate-methacrylic acid copolymer, styrene-methyl methacrylate-acrylic acid copolymer , styrene-methyl methacrylate-acrylonitrile copolymer, styrene-methyl methacrylate-methacrylonitrile copolymer, styrene and methyl methacrylate and N-phenylmaleimide Copolymers, copolymers of styrene, methyl methacrylate and N-cyclohexylmaleimide, vinyl chloride resins, alicyclic polyolefin resins, etc. Examples of polyester resins other than the above polyester resin (a) specifically include polyethylene terephthalate, polyethylene naphthalate, and isophthalic acid-modified polyethylene terephthalate. Ethylene glycol ester, 1,4-cyclohexanedimethanol modified polyethylene terephthalate, polyarylate, etc. The above-mentioned other resin components may be used alone or in combination of two or more. The proportion of other resin components in the acrylic resin composition is less than 10% by weight.

The polymerization methods of the methyl methacrylate-styrene copolymer (d) and the styrene-maleic anhydride copolymer (e) used in the present invention are not particularly limited, but radical polymerization using an organic peroxide is preferred. As the production process, an overall continuous polymerization process using a small amount of solvent is preferable. The method obtained by the process of suspension polymerization or emulsion polymerization may not be able to obtain sufficient transparency. As organic peroxides added during polymerization, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, 1,1-bis(tert-butylperoxy)-3,3, 5-trimethylcyclohexane, 1,1-bis(tert-butylperoxycyclohexyl)-cyclohexane, 2,2-bis(4,4-dibutylperoxycyclohexyl)propane, tert-butylperoxy Known substances such as isopropyl monocarbonate oxide, di-tert-butyl peroxide, dicumyl peroxide, and ethyl-3,3-bis(tert-butylperoxy)butyrate. It is preferable that the addition amount of an organic peroxide is 0.001-5 weight part with respect to a total of 100 weight part of monomers. As the solvent, aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane; cyclopentane, methylcyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons such as hexane and ethylcyclohexane; or aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, etc., the addition amount of the solvent is preferably 5 parts by weight relative to the total of 100 parts by weight of the monomers. ~20 parts by weight. In addition, there is no problem in adding a known molecular weight modifier such as 4-methyl-2,4-diphenylpentene-1, t-dodecylmercaptan, or n-dodecylmercaptan during polymerization. The polymerization temperature is preferably 80 to 170°C, more preferably 100 to 160°C.

In the above-mentioned acrylic resin composition, relative to the total of at least one selected from the group consisting of acrylic resin (c) and methyl methacrylate-styrene copolymer (d) and styrene-maleic anhydride copolymer (e) , The ratio of the styrene-maleic anhydride copolymer (e) is preferably 1 to 35% by weight. When the styrene-maleic anhydride copolymer (e) is less than 1% by weight, the dimensional stability in a high-temperature, high-humidity environment decreases, and when it exceeds 35% by weight, the scratch resistance decreases. By making it into the above-mentioned composition, heat resistance and moisture absorption can be improved without deteriorating the scratch resistance of the layer (B) containing an acrylic resin composition, and the thermoplastic resin laminated body of this invention can acquire scratch resistance. Excellent performance and dimensional stability in high-temperature and high-humidity environments. With respect to the total of at least one selected from acrylic resin (c) and methyl methacrylate-styrene copolymer (d) and styrene-maleic anhydride copolymer (e), styrene-maleic anhydride copolymer The ratio of the substance (e) is more preferably in the range of 5 to 30% by weight.

The ratio of the structural unit derived from methyl methacrylate to the total of the structural unit derived from methyl methacrylate, the structural unit derived from styrene, and the structural unit derived from maleic anhydride in the above-mentioned acrylic resin composition is preferably 70 to 95 mol%, and the proportion of structural units derived from maleic anhydride is preferably 1 to 5 mol%. When the ratio of these structural units in the acrylic resin composition is within the above range, the thermoplastic resin laminate of the present invention has excellent dimensional stability and scratch resistance in a high-temperature, high-humidity environment. The ratio of the structural unit derived from methyl methacrylate to the total of the structural unit derived from methyl methacrylate, the structural unit derived from styrene, and the structural unit derived from maleic anhydride is more preferably 70 to 90 mol%. In addition, the ratio of the structural unit derived from styrene to the total of the structural unit derived from methyl methacrylate, the structural unit derived from styrene, and the structural unit derived from maleic anhydride in the above-mentioned acrylic resin composition is preferably 4. ~29 mol%, more preferably 5-25 mol%.

The aforementioned thermoplastic resin composition and/or the aforementioned acrylic resin composition may contain various additives. Examples of the above-mentioned various additives include antioxidants, ultraviolet absorbers, anti-coloring agents, antistatic agents, mold release agents, lubricants, dyes, pigments, inorganic fillers, resin fillers, and the like. The method of mixing is not particularly limited, and a method of blending a total amount, a method of dry blending masterbatches, a method of dry blending a total amount, and the like can be used.

The above-mentioned thermoplastic resin composition can be produced by known techniques. It does not specifically limit, For example, it can obtain by melt-kneading after dry mixing the component containing polyester resin (a) and polycarbonate resin (b). The above-mentioned acrylic resin composition can also be obtained by the same method.

The thermoplastic resin laminate of the present invention has a layer (A) containing a thermoplastic resin composition and a layer (B) provided on at least one surface of the layer (A) and containing an acrylic resin composition.

As a method for producing the thermoplastic resin laminate of the present invention, known lamination techniques such as coextrusion method, coextrusion lamination method, extrusion lamination method, and dry lamination method can be used. In addition, for these laminations, an appropriate adhesive or adhesive resin may be used between the resins.

The type and layer structure (stacking order, number of layers) of the layer (A) containing a thermoplastic resin composition and the multilayered layer (B) containing an acrylic resin composition may be selected according to the application. For example, in an application that requires both surface hardness and dimensional stability in a high-temperature, high-humidity environment, it is possible to use a layer (B) containing an acrylic resin composition for the surface layer and a thermoplastic resin composition for the center layer. Two kinds of two-layer layer structures (layer (B) containing acrylic resin composition/layer (A) containing thermoplastic resin composition) of the layer (A) and two kinds of three-layer layer structures (containing acrylic resin layer (B) of the composition/layer (A) comprising the thermoplastic resin composition/layer (B) comprising the acrylic resin composition) to obtain transparency, heat resistance, scratch resistance, impact resistance and high temperature A thermoplastic resin laminate excellent in dimensional stability in a high-humidity environment.

The thickness of the thermoplastic resin laminate in the present invention is preferably in the range of 0.1 to 10.0 mm. If it is less than 0.1 mm, poor transfer or poor thickness accuracy may occur due to back-through. In addition, if it exceeds the range of 10.0 mm, poor thickness accuracy or poor appearance may occur due to uneven cooling after molding. It is more preferably in the range of 0.3 to 5.0 mm, and still more preferably in the range of 0.3 to 3.0 mm.

The thickness (one side) of the layer (B) containing the acrylic resin composition in the thermoplastic resin laminate of the present invention is preferably 25% or less of the thickness of the entire thermoplastic resin laminate, preferably in the range of 10 to 500 μm. When the thickness (one side) of the layer (B) exceeds 25% of the thickness of the entire thermoplastic resin laminate, warping may occur in a high-temperature, high-humidity environment. In addition, when the range is less than 10 μm, scratch resistance and weather resistance may be insufficient, and when the range exceeds 500 μm, warping may occur in a high-temperature, high-humidity environment. More preferably, it is the range of 30-200 micrometers.

A hard coat treatment can be given to one surface or both surfaces of the thermoplastic resin laminate of this invention. For example, the hard coat layer is formed by using a photosensitive hard coat paint cured by light energy. As a photosensitive hard coat curable by light energy, photocurable hard coatings obtained by adding a photopolymerization initiator to a resin composition containing monofunctional and/or polyfunctional acrylate monomers and/or oligomers can be cited. resin composition, etc. For example, a methacrylate compound ( f2) A photocurable resin composition obtained by adding 1 to 10 parts by weight of a photopolymerization initiator (f3) to 100 parts by weight of a resin composition of 20 to 40% by weight.

The method of applying the hard coat in the present invention is not particularly limited, and known methods can be used. For example, brush coating, gravure roll coating, dip coating, pour coating, spray coating, inkjet coating, etc. are mentioned.

Any one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment, and anti-glare treatment can be applied to one or both surfaces of the synthetic resin laminate of the present invention. Methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and anti-glare treatment are not particularly limited, and known methods can be used. For example, a method of applying an antireflective paint, a method of vapor-depositing a dielectric thin film, a method of applying an antistatic paint, and the like can be mentioned.

The thermoplastic resin laminate of the present invention preferably has a total light transmittance of 90% or more at a thickness of 1.0 mm.

The thermoplastic resin laminate of a preferred embodiment of the present invention is characterized by excellent transparency, heat resistance, scratch resistance, and dimensional stability in a high-temperature and high-humidity environment, and the thermoplastic resin laminate can be used as a transparent substrate material, Transparency protection materials, etc., are especially suitable for front panels of display devices that require high dimensional stability in high-temperature and high-humidity environments.

Example

Hereinafter, the present invention will be specifically described by way of examples. However, the scope of the present invention is not limited by these Examples.

Polyester resin (a), methyl methacrylate-styrene copolymer (d), styrene-maleic anhydride copolymer (e), evaluation of acrylic resin composition, thermoplastic properties obtained from Examples and Comparative Examples The evaluation of the resin laminate was performed as follows.

<Structure Analysis of Resin Components>

Regarding the structural determination of polyester resin (a), methyl methacrylate-styrene copolymer (d), and styrene-maleic anhydride copolymer (e), 20 mg of the resin was dissolved in 1 g of deuterated chloroform, and the -NMR measurement, calculated from the area ratio of the peaks. As a measuring device, JNM-AL400 manufactured by JEOL Ltd. was used, and the measurement was performed at 400 MHz.

<Measurement of Average Molecular Weight>

Regarding the molecular weight (number average molecular weight Mn, weight average molecular weight Mw, molecular weight distribution Mw/Mn), 2 mg of the resin was dissolved in 20 g of chloroform, and the gel permeation chromatography (GPC) was used to measure the value in terms of standard polystyrene As Mn, Mw, Mw/Mn. Regarding GPC, two columns GMHHR-L and one TSK G5000HR column manufactured by TOSOH Co., Ltd. were connected to TOSOH 8020 manufactured by TOSOH Co., Ltd., and the measurement was performed at a column temperature of 40°C. For the eluent, chloroform was injected at a flow rate of 1.0 ml/min, and measurement was performed using a UV detector.

<Evaluation of Component Molar Ratio of Acrylic Resin Composition>

The structural unit derived from methyl methacrylate in the layer (B) containing the acrylic resin composition of the thermoplastic resin laminate obtained in the following Examples and Comparative Examples (hereinafter referred to simply as " MMA units"), structural units derived from styrene (hereinafter referred to simply as "St units"), and structural units derived from maleic anhydride (hereinafter referred to as "MAH units") were analyzed for their molar ratios.

Regarding the component molar ratio, only 20 mg of the acrylic resin composition was scraped off from the layer (B) of the thermoplastic resin laminate, dissolved in 1 g of deuterated chloroform, measured by 13C-NMR (i.g.), and calculated from the area ratio of the peaks . As a measuring device, AVANCE II manufactured by Bruker Biospin Co., Ltd. was used, and the measurement was performed at 600 MHz. The molar ratios of MMA units, St units, and MAH units in the acrylic resin compositions of the thermoplastic resin laminates obtained in Examples and Comparative Examples are shown in Table 1, respectively.

<Transparency evaluation>

For the thermoplastic resin laminates obtained in the following examples and comparative examples, the total light transmittance was measured using a colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd.: COH-400) in accordance with JIS K 7105 and ASTM D1003. determined. A laminate having a total light transmittance of 90% or more at a thickness of 1.0 mm was rated as acceptable.

<Heat Resistance Evaluation>

For the thermoplastic resin laminates obtained in the following examples and comparative examples, a rectangle with a length of 90 mm and a width of 60 mm was cut out from a thermoplastic resin laminate with a thickness of 1.0 mm, with the extrusion direction being the longitudinal direction and the width direction being the transverse direction. For the test piece, clamp the portion up to 5 mm from the center of the short side with a clip with a width of 13 mm, hang the test piece in a vertical state, and heat it in an oven set at 90° C. for 48 hours. After the test, the test piece was placed on a horizontal plane in such a way that the upper surface was depressed, and a φ38mm, 300g weight was placed in the center of the test piece and fixed, and the deformation of the gap length between the four corners of the test piece and the horizontal plane was measured. , and the laminate whose total deformation amount does not exceed 0.5 mm is regarded as acceptable.

<Evaluation of Scratch Resistance>

With regard to the thermoplastic resin laminates obtained in the following examples and comparative examples, pencil hardness according to JIS K 5600-5-4, using pencils of various hardness (Mitsubishi Pencil Co., Ltd. manufactured UNI) The pencil hardness of layer (B) of the composition was determined. A laminate having a pencil hardness of 3H or more was rated as a pass.

<Impact resistance test>

Regarding the thermoplastic resin laminates obtained in the following examples and comparative examples, with regard to impact resistance, the layer (B) containing the acrylic resin composition is the upper side, and the layer (A) containing the thermoplastic resin composition is the lower side. side, was evaluated by the falling ball test. In the falling ball test, the sample is fixed between the flanges of φ50, the metal ball of φ25 and 63.7g is dropped, and the height of the test piece installed at the bottom is measured at 10cm intervals, and the height of the fracture is the highest measured to 150cm. The laminated body whose height at the time of fracture was 100 cm or more was judged as a pass.

<Evaluation of Dimensional Stability in High Temperature and High Humidity Environment>

For the thermoplastic resin laminates obtained in the following examples and comparative examples, a rectangular test of 90 mm in length and 60 mm in width was cut out from a thermoplastic resin laminate having a thickness of 1.0 mm, with the extrusion direction being the longitudinal direction and the width direction being the transverse direction. For the piece, clamp the part up to 5 mm from the center of the short side with a clip with a width of 13 mm, hang the test piece in a vertical state, and heat it for 120 hours in a constant temperature and humidity machine set at a temperature of 85°C and a humidity of 85%. After the test, the test piece was placed on a horizontal plane in such a way that the upper surface was depressed, and a φ38mm, 300g weight was placed in the center of the test piece and fixed, and the deformation of the gap length between the four corners of the test piece and the horizontal plane was measured. , and the laminated body whose total value of the deformation does not exceed 0.5 mm was regarded as a pass.

<Moldability Evaluation>

For the thermoplastic resin laminates obtained in the following examples and comparative examples, a rectangular test of 90 mm in length and 60 mm in width was cut out from a thermoplastic resin laminate having a thickness of 1.0 mm, with the extrusion direction being the longitudinal direction and the width direction being the transverse direction. The sheet was adjusted to a temperature of 23° C. and a humidity of 50%. After the test, the test piece was placed on a horizontal plane in a way that the upper surface was depressed, and a heavy object with a diameter of 38mm and a weight of 300g was placed in the center of the test piece and fixed, and the deformation of the gap length between the four corners of the test piece and the horizontal plane was measured. The laminated body whose total deformation amount did not exceed 0.3 mm was rated as acceptable.

[Synthesis Example 1]

Dimethyl terephthalate is used as the dicarboxylic acid component, and 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10 is used as the diol component -tetraoxaspiro[5.5]undecane and ethylene glycol are respectively 45 mol% and 55 mol% of the raw material monomers, and when 0.03 moles of manganese acetate tetrahydrate is present with respect to 100 moles of the dicarboxylic acid component, The temperature was raised to 200° C. under a nitrogen atmosphere to carry out a transesterification reaction. After the distilled amount of methanol reached 90% or more relative to the theoretical amount, 0.01 mole of antimony (III) oxide and 0.06 mole of triphenyl phosphate were added to 100 moles of the dicarboxylic acid component, and the temperature was raised and reduced gradually, and finally at Polymerization is carried out at 280°C and below 0.1MPa. The reaction is terminated at the point when a moderate melt viscosity is reached, and a polyester resin (a) is obtained. The proportion of diol units having a cyclic acetal skeleton in the obtained polyester resin (a) was 45 mol%, Mn was 16500, and Mw/Mn was 3.6.

[Synthesis Example 2]

A fully mixed reactor with a volume of about 20 liters with a stirrer, a tower plug flow reactor with a volume of about 40 liters, and a devolatilization tank with a preheater are connected in series. Prepare the monomer mixed solution containing 11 mass parts of styrene, 89 mass parts of methyl methacrylate, and 8 mass parts of ethylbenzene, in addition, mix 1,1-bis (tert-butyl peroxide)-cyclohexane (Japan 0.02 parts by mass of PERHEXA C) manufactured by Oil & Fat Co., Ltd. and 0.02 parts by mass of n-dodecyl mercaptan (THIOKALCOL 20 manufactured by Kao Corporation) were used to prepare a raw material solution. This raw material solution was introduced at 6 kg per hour into a complete mixing reactor whose temperature was controlled at 130°C. In addition, it implemented at the stirring speed of a complete mixing type reactor 180rpm. Next, the reaction solution was continuously taken out from the complete mixing reactor, and introduced into a tower plug flow reactor adjusted to have a temperature gradient from 130°C to 160°C along the flow direction. While heating this reaction liquid using a preheater, it was introduced into a devolatilizer controlled at a temperature of 235° C. and a pressure of 1.0 kPa, and volatile components such as unreacted monomers were removed. This resin solution was taken out with a gear pump to obtain a methyl methacrylate-styrene copolymer (d). The ratio of the methyl methacrylate unit of the obtained methyl methacrylate-styrene copolymer (d) was 89 weight%, the ratio of the styrene unit was 11 weight%, Mn was 17000, and Mw/Mn was 2.4.

[Synthesis Example 3]

Making the monomer mixed solution 84 parts by mass of styrene, 16 parts by mass of maleic anhydride, and making the n-dodecanethiol added to the raw material solution 0.2 parts by mass, except that, it was carried out in the same manner as in Synthesis Example 2, and obtained Styrene-maleic anhydride-based copolymer (e). The obtained styrene-maleic anhydride copolymer (e) contained 84 weight% of styrene units, 16 weight% of maleic anhydride units, Mn=17000, and Mw/Mn=2.4.

[Example 1]

Use the multi-layer extruding device that has the uniaxial extruder of shaft diameter 32mm, the uniaxial extruder of shaft diameter 65mm, the feed unit that is connected with full extruder and the T die head with feed unit, be shaped as Thermoplastic resin laminated board. Acrylic resin [manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: DELPET 80NH] (c) and the methyl methacrylate-styrene copolymer obtained in Synthesis Example 2 were continuously introduced into a single-screw extruder with a shaft diameter of 32 mm. (d) The styrene-maleic anhydride copolymer obtained in Synthesis Example 3 (e) is the propylene-based resin mixture obtained by dry mixing the respective weight ratios of 90:2.5:7.5. Extruded at a speed of 4.8kg/h. In addition, the polyester resin (a) and polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: IUPILON S-3000] obtained in Synthesis Example 1 were continuously introduced into a single-screw extruder with a shaft diameter of 65 mm. (b) The thermoplastic resin mixtures obtained by dry mixing at a weight ratio of 60:40 were extruded at a cylinder temperature of 260° C. and a discharge speed of 67 kg/h. The feeding unit connected to the full extruder was equipped with two types of two-layer diverter needles, and the acrylic resin composition (B1) layer was introduced into one side of the thermoplastic resin composition (A1) layer at a temperature of 260°C for lamination. It was extruded into a sheet with a T-die with a temperature of 260°C connected to the front end, and cooled while transferring the mirror surface with 3 polishing rollers to obtain an acrylic layer laminated on one side of the thermoplastic resin composition (A1) layer. A thermoplastic resin laminate of a resin composition (B1) layer. The set temperatures of the rolls at this time were 85°C, 85°C, and 107°C in order from the upstream side. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B1) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability in a high-temperature and high-humidity environment, and moldability evaluation were respectively good, and the overall judgment was acceptable.

[Example 2]

Instead of the acrylic resin composition (B1) used in Example 1, an acrylic resin [manufactured by Asahi Chemicals Co., Ltd., trade name: DELPET 80NH] (c), methyl methacrylate-styrene copolymer (d ), styrene-maleic anhydride copolymer (e) is the propylene-based resin mixture obtained by dry mixing in a weight ratio of 80:5:15, except that, the same operation as in Example 1 is obtained to obtain the thermoplastic resin composition A thermoplastic resin laminate in which an acrylic resin composition (B2) layer is laminated on one surface of the (A1) layer. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation under high temperature and high humidity environment, and moldability evaluation were respectively good, and the overall judgment was acceptable.

[Example 3]

Instead of the acrylic resin composition (B1) used in Example 1, an acrylic resin [manufactured by Asahi Chemicals Co., Ltd., trade name: DELPET 80NH] (c), methyl methacrylate-styrene copolymer (d ), styrene-maleic anhydride copolymer (e) is 70: 7.5: 22.5 dry-mixed propylene-based resin mixture obtained with respective weight ratios, except that, operate in the same manner as in Example 1 to obtain the thermoplastic resin composition A thermoplastic resin laminate in which an acrylic resin composition (B3) layer is laminated on one surface of the (A1) layer. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B3) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation under high temperature and high humidity environment, and moldability evaluation were respectively good, and the overall judgment was acceptable.

[Example 4]

Instead of the acrylic resin composition (B1) used in Example 1, an acrylic resin [manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: DELPET 80NH] (c), a styrene-maleic anhydride copolymer (e) and The respective weight ratios were 90:10 dry-mixed propylene-based resin mixtures, except that, in the same manner as in Example 1, one side of the thermoplastic resin composition (A1) layer was laminated with an acrylic resin composition ( B4) layered thermoplastic resin laminate. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B4) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation under high temperature and high humidity environment, and moldability evaluation were respectively good, and the overall judgment was acceptable.

[Example 5]

Instead of the thermoplastic resin composition (A1) used in Example 2, polyester resin (a), carbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: IUPILON S-3000] (b) were used in respective weights Except for the thermoplastic resin mixture obtained by dry mixing at a ratio of 90:10, the same operation as in Example 2 was performed to obtain a layer having an acrylic resin composition (B2) laminated on one side of the thermoplastic resin composition (A2) layer. thermoplastic resin laminates. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation under high temperature and high humidity environment, and moldability evaluation were respectively good, and the overall judgment was acceptable.

[Example 6]

Instead of the thermoplastic resin composition (A1) used in Example 2, polyester resin (a) and polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: IUPILON S-3000] (b) were used respectively Except for the thermoplastic resin mixture obtained by dry mixing at a weight ratio of 75:25, the same operation as in Example 2 was performed to obtain an acrylic resin composition (B2) laminated on one side of the thermoplastic resin composition (A3) layer. layered thermoplastic resin laminate. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation under high temperature and high humidity environment, and moldability evaluation were respectively good, and the overall judgment was acceptable.

[Example 7]

Instead of the thermoplastic resin composition (A1) used in Example 2, polyester resin (a) and polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: IUPILON S-3000] (b) were used respectively The thermoplastic resin mixture obtained by dry mixing at a weight ratio of 50:50 was carried out in the same manner as in Example 2 except that the acrylic resin composition (B2) was laminated on one side of the thermoplastic resin composition (A4) layer. layered thermoplastic resin laminate. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation under high temperature and high humidity environment, and moldability evaluation were respectively good, and the overall judgment was acceptable.

[Example 8]

Instead of the thermoplastic resin composition (A1) used in Example 3, polyester resin (a) and polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: IUPILON S-3000] (b) were used respectively Except for the thermoplastic resin mixture obtained by dry mixing at a weight ratio of 90:10, the same operation as in Example 3 was performed to obtain an acrylic resin composition (B3) laminated on one side of the thermoplastic resin composition (A2) layer. layered thermoplastic resin laminate. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B3) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation under high temperature and high humidity environment, and moldability evaluation were respectively good, and the overall judgment was acceptable.

[Comparative example 1]

In place of the acrylic resin composition (B1) used in Example 1, an acrylic resin [manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: DELPET 80NH] (c) was used, and the same procedure as in Example 1 was used to obtain the A thermoplastic resin laminate in which the acrylic resin (c) layer is laminated on one surface of the thermoplastic resin composition (A1) layer. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, and moldability evaluation were respectively good, but the results of dimensional stability evaluation under high-temperature and high-humidity environment were poor, and the overall judgment was unacceptable .

[Comparative example 2]

Instead of the acrylic resin composition (B1) used in Example 1, an acrylic resin [manufactured by Asahi Chemicals Co., Ltd., trade name: DELPET 80NH] (c), methyl methacrylate-styrene copolymer (d ), styrene-maleic anhydride copolymer (e) is 50: 12.5: 37.5 dry-mixed propylene-based resin mixture obtained with respective weight ratios, except that, operate in the same manner as in Example 1 to obtain the thermoplastic resin composition A thermoplastic resin laminate in which an acrylic resin composition (B5) layer is laminated on one surface of the (A1) layer. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B5) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of heat resistance evaluation, impact resistance evaluation, dimensional stability evaluation under high temperature and high humidity environment, and moldability evaluation were respectively good, but the results of transparency evaluation and scratch resistance evaluation were poor, and the overall judgment was unacceptable .

[Comparative example 3]

Instead of the acrylic resin composition (B2) used in Example 5, an acrylic resin [manufactured by Asahi Chemicals Co., Ltd., trade name: DELPET 80NH] (c), methyl methacrylate-styrene copolymer (d ), styrene-maleic anhydride copolymer (e) is 50: 12.5: 37.5 dry-mixed propylene-based resin mixture obtained with respective weight ratios, except that, operate in the same way as in Example 5 to obtain the thermoplastic resin composition The thermoplastic resin laminate in which the acrylic resin composition (B5) layer is laminated on one surface of the (A2) layer. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B5) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of heat resistance evaluation, impact resistance evaluation, and formability evaluation were respectively good, but the results of transparency evaluation, scratch resistance evaluation, and dimensional stability evaluation under high temperature and high humidity environment were poor, and the overall judgment was unacceptable .

[Comparative example 4]

In place of the thermoplastic resin composition (A1) used in Example 2, polyester resin (a) was used, and the same procedure as in Example 1 was performed except that acrylic acid was laminated on one side of the polyester resin (a) layer. A thermoplastic resin laminate having a layer similar to the resin composition (B2). The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, and moldability evaluation were respectively good, but the results of dimensional stability evaluation under high-temperature and high-humidity environment were poor, and the overall judgment was unacceptable .

[Comparative Example 5]

In place of the thermoplastic resin composition (A1) used in Example 2, a polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: IUPILON S-3000] (b) was used, except that it was the same as in Example 1 This operation gave a thermoplastic resin laminate in which the acrylic resin composition (B2) layer was laminated on one surface of the polycarbonate resin (b) layer. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 μm near the center.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, impact resistance evaluation, and dimensional stability evaluation under high-temperature and high-humidity environment were respectively good, but the results of scratch resistance evaluation and moldability evaluation were poor, and the overall judgment was unacceptable .

[Comparative Example 6]

It was molded into a thermoplastic resin sheet using a single-layer extrusion device having a single-screw extruder with a shaft diameter of 65 mm and a T-die. The polyester resin (a) was continuously introduced into a single-screw extruder with a shaft diameter of 65 mm, and extruded at a barrel temperature of 250° C. and a discharge rate of 70 kg/h. It was extruded into a sheet form with a T-die at 250° C. connected to the front end, and cooled while transferring the mirror surface with three polishing rolls to obtain a thermoplastic resin sheet of polyester resin (a). The obtained thermoplastic resin plate had a thickness of 1.0 mm.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, impact resistance evaluation, and moldability evaluation were respectively good, but the results of scratch resistance evaluation and dimensional stability evaluation under high temperature and high humidity environment were poor, and the overall judgment was unacceptable .

[Comparative Example 7]

In place of the polyester resin (a) used in Comparative Example 6, a polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: IUPILON S-3000] (b) was used, and the same procedure as in Comparative Example 6 was used. , to obtain a thermoplastic resin plate of polycarbonate resin (b). The obtained thermoplastic resin plate had a thickness of 1.0 mm.

The evaluation results are shown in Table 1. The results of heat resistance evaluation, impact resistance evaluation, and dimensional stability evaluation in high-temperature and high-humidity environments were respectively good, but the results of transparency evaluation, scratch resistance evaluation, and moldability evaluation were poor, and the overall judgment was unacceptable .

[Comparative Example 8]

In place of the polyester resin (a) used in Comparative Example 6, an acrylic resin [manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: DELPET 80NH] (c) was used, and an acrylic resin ( c) thermoplastic resin plate. The obtained thermoplastic resin plate had a thickness of 1.0 mm.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, and moldability evaluation were respectively good, but the results of impact resistance evaluation and dimensional stability evaluation under high temperature and high humidity environment were poor, and the overall judgment was unacceptable .

[Comparative Example 9]

In place of the polyester resin (a) used in Comparative Example 6, a methyl methacrylate-styrene copolymer (d) was used, and a methyl methacrylate-styrene copolymer was obtained in the same manner as in Comparative Example 6. The thermoplastic resin plate of thing (d). The obtained thermoplastic resin plate had a thickness of 1.0 mm.

The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, and moldability evaluation were respectively good, but the results of scratch resistance evaluation, impact resistance evaluation, and dimensional stability evaluation under high temperature and high humidity environment were poor, and the overall judgment was unacceptable .

[Comparative Example 10]

In place of the polyester resin (a) used in Comparative Example 6, except that a styrene-maleic anhydride copolymer (e) was used, the same procedure as in Comparative Example 6 was performed to obtain a styrene-maleic anhydride copolymer (e) thermoplastic resin board. The obtained thermoplastic resin plate had a thickness of 1.0 mm.

The evaluation results are shown in Table 1. The results of heat resistance evaluation, dimensional stability evaluation under high-temperature and high-humidity environment, and moldability evaluation were respectively good, but the results of transparency evaluation, scratch resistance evaluation, and impact resistance evaluation were poor, and the overall judgment was unacceptable .

[Table 1]

Claims (8)

1. a thermoplastic resin laminate, it is characterised in that:

There is the layer (A) comprising thermoplastic resin composition and be arranged at described layer (A) extremely Lack a face and the layer (B) comprising acrylic resin composition,

Described thermoplastic resin composition contains polyester resin (a) and polycarbonate resin (b), This polyester resin (a) contains dihydroxylic alcohols construction unit and dicarboxylic acid structural units, wherein, all 10～60 moles of % in dihydroxylic alcohols construction unit are from shown in following formula (1) or following formula (2) The dihydroxylic alcohols construction unit of the dihydroxylic alcohols with cyclic acetal skeleton, relative to described thermoplastic Property resin combination in polyester resin (a) and the total of polycarbonate resin (b), poly-carbon The ratio of acid ester resin (b) is 5～50 weight %,

In formula (1) and (2), R¹、R²And R³Independently, represent selected from carbon number and be The aliphatic group of 1～10, carbon number be 3～10 ester ring type group and carbon number be The organic group of the aromatic group of 6～10,

Described acrylic resin composition contains selected from acrylic resin (c) and methacrylic acid At least one in methyl ester-styrol copolymer (d) and styrene-maleic anhydride copolymer E (), relative to the knot from methyl methacrylate in described acrylic resin composition Structure unit, from cinnamic construction unit and the total of the construction unit from maleic anhydride, Ratio from the construction unit of methyl methacrylate is 70～95 moles of %, from maleic acid The ratio of the construction unit of acid anhydride is 1～5 mole of %.

2. thermoplastic resin laminate as claimed in claim 1, it is characterised in that:

Relative in described styrene-maleic anhydride copolymer (e) from cinnamic structure Unit and the total of the construction unit from maleic anhydride, from the ratio of cinnamic construction unit Example is 75～95 weight %.

3. thermoplastic resin laminate as claimed in claim 1 or 2, it is characterised in that:

The described dihydroxylic alcohols with cyclic acetal skeleton is the double (1,1-dimethyl-2-hydroxyl second of 3,9- Base)-2,4,8,10-four oxaspiro [5.5] hendecane.

4. the thermoplastic resin laminate as according to any one of claims 1 to 3, its feature exists In:

In described polyester resin (a), in whole dicarboxylic acid structural units from terephthaldehyde The ratio of the construction unit of acid is 70 moles of more than %.

5. the thermoplastic resin laminate as according to any one of Claims 1 to 4, its feature exists In:

One face or two faces are implemented hard conating and process.

6. the thermoplastic resin laminate as according to any one of Claims 1 to 5, its feature exists In:

One face or two faces are implemented at antireflection process, antifouling process, antistatic Any one above process in reason, weatherability treatment and anti-dazzle process.

7. a transparent substrate material, it is characterised in that:

Comprise the thermoplastic resin laminate according to any one of claim 1～6.

8. a transparency protection material, it is characterised in that:

Comprise the thermoplastic resin laminate according to any one of claim 1～6.