Thermoplastic polymer composition, sheet or film, laminate, and method for producing same

Abstract

The present invention addresses the problem of providing a thermoplastic polymer composition that can be shaped into a highly transparent sheet or film exhibiting low anisotropy, and that has good sheet or film shape formability.

Description

Thermoplastic polymer composition, sheet or film, laminate and method for producing same

[0001] This patent application claims priority under the Paris Convention to Japanese Patent Application No. 2024-072203 (filing date: April 26, 2024), the entire contents of which are incorporated herein by reference. The present invention relates to a thermoplastic polymer composition. The present invention also relates to a sheet or film using the thermoplastic polymer composition, a laminate, a method for producing the same, and a paint protection sheet or film including the laminate.

[0002] Paint protection films, chip-resistant films, and vehicle exterior protective films are used to protect the painted surfaces and bodies of automobiles from flying stones, scratches, dirt, etc. Such protective films for the exterior of automobiles and other vehicles are required to have flexibility, scratch resistance, high transparency, and weather resistance and durability sufficient to withstand long-term outdoor use. These protective films are widely made of polyurethane resins as the substrate.

[0003] However, polyurethane resins are expensive and subject to cost constraints, and therefore, efforts are being made to replace polyurethane resin substrates with resins such as thermoplastic elastomers. On the other hand, when molded into films or sheets, those that are weak against tension in a specific direction have problems in terms of handling.

[0004] Among thermoplastic elastomers, styrene-based thermoplastic elastomers, such as styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), and hydrogenated products thereof, are widely used in a variety of applications due to their low cost and excellent flexibility, rubber elasticity, and recyclability, and are also used as a substitute for polyurethane resin substrates in vehicle exterior protective films (see Patent Document 1). Furthermore, among styrene-based thermoplastic elastomers, block copolymers in which the styrene block is replaced with a polymer block mainly composed of α-methylstyrene have excellent scratch resistance and abrasion resistance, and it is known that when mixed with an acrylic resin, a thermoplastic polymer composition can be obtained that combines good moldability, flexibility, and rubber elasticity, and has scratch resistance and abrasion resistance comparable to those of polyurethane-based thermoplastic elastomers and polyester-based thermoplastic elastomers, while also exhibiting improved transparency and mechanical properties when formed into a sheet or film (see Patent Document 2).

[0005] JP 2023-150863 A, Patent No. 5736529

[0006] The surface protection film of Patent Document 1 is said to have excellent workability, flexibility, and elongation without using a polyurethane resin, but as a result of studies by the present inventors, it has been found to have problems such as poor transparency when an adhesive layer is provided, excessively high flexibility resulting in poor workability due to differences in feel, and film thickness fluctuations occurring during film molding, making it difficult to obtain a uniform film, particularly at a thickness of 300 μm or less. Furthermore, while the composition of Patent Document 2 is said to have excellent moldability, as a result of studies by the present inventors, it has been found to have problems such as anisotropy occurring in the film when film molding is performed at low temperatures, resulting in a large difference in tear strength between the MD and TD directions, and film thickness fluctuations occurring when film molding is performed at high temperatures to eliminate the anisotropy of the film, making it difficult to obtain a uniform film, particularly at a thickness of 300 μm or less.

[0007] An object of the present invention is to provide a thermoplastic polymer composition which can be molded into a sheet or film having high transparency and low anisotropy, and which also has good processability for molding into a sheet or film.

[0008] As a result of extensive investigations, the present inventors have found that the above-mentioned problems can be solved by adding specific amounts of an acrylic resin having a relatively low degree of polymerization and an acrylic resin having a relatively high degree of polymerization to a block copolymer containing a polymer block mainly composed of α-methylstyrene units. Based on this finding, further investigations have led to the completion of the present invention. The present invention can be configured in the following aspects. [Aspect 1] A block copolymer (I) containing a polymer block P mainly composed of α-methylstyrene units and a hydrogenated or non-hydrogenated polymer block Q mainly composed of conjugated diene or isobutylene units and having a weight average molecular weight of 30,000 to 200,000, an acrylic resin (II) containing 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith and having an average degree of polymerization of 400 to 2,000, an acrylic resin (III) containing 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith and having an average degree of polymerization of 6,000 to 40,000, and a softener (IV) are reacted in a manner such that: 0.1≦W(II) / W(I)≦2.4 (a) 0.001≦W(III) / (W(I)+W(II))≦0.04 (b) 0≦W(IV) / (W(I)+W(II)+W(III)+W(IV))≦0.5 (c) [wherein W(I), W(II), W(III) and W(IV) represent the contents (by mass) of the block copolymer (I), acrylic resin (II), acrylic resin (III) and softener (IV) in the thermoplastic polymer composition, respectively].[Aspect 2] A thermoplastic polymer composition comprising a block copolymer (I) having a weight-average molecular weight of 30,000 to 200,000, which comprises a polymer block P mainly composed of α-methylstyrene units and a hydrogenated or non-hydrogenated polymer block Q mainly composed of conjugated diene or isobutylene units, an acrylic resin (II) containing 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith, and having an average degree of polymerization of 400 to 2,000, an acrylic resin (III) containing 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith, and having an average degree of polymerization of 6,000 to 40,000, and a softener (IV), wherein the film thickness variation coefficient measured in accordance with JIS K 7130:1999 using a film extruded to a thickness of 150 μm is 5% or less, and A thermoplastic polymer composition having both 400 N / cm or more in tear strength in the MD direction and 400 N / cm or more in tear strength in the TD direction at room temperature, as measured using an unnotched angle-shaped test piece in accordance with JIS J 6252-1:2015. [Aspect 3] The thermoplastic polymer composition according to Aspect 1 or 2, wherein the acrylic resin (II) has a melt flow rate of 5 to 25 g / 10 min at 230°C and 37.3 N. [Aspect 4] The thermoplastic polymer composition according to any one of Aspects 1 to 3, wherein the strand breaks at a tension of 30 kPa or more when extruded from a capillary having a diameter of 1 mm and a length of 10 mm at an extrusion temperature of 230°C at a piston speed of 5 mm / min using a melt tension measurement device of a capillary rheometer. [Aspect 5] The thermoplastic polymer composition according to any one of Aspects 1 to 4, wherein the strand breaks at a rate of 40 m / min or more when extruded at a piston speed of 5 mm / min from a 1 mm diameter and 10 mm long capillary at an extrusion temperature of 230° C. using a melt tension measurement device of a capillary rheometer and withdrawn. [Aspect 6] The thermoplastic polymer composition according to any one of Aspects 1, 3 to 5, wherein the tear strength in the MD direction and the tear strength in the TD direction at room temperature are both 400 N / cm or more when measured using a film formed to a thickness of 150 μm in an extruder using an unnotched angle-shaped test piece in accordance with JIS K 6252-1:2015.[Aspect 7] A sheet or film made of the thermoplastic polymer composition according to any one of Aspects 1 to 6. [Aspect 8] A block copolymer (I) containing a polymer block P mainly composed of α-methylstyrene units and a hydrogenated or unhydrogenated polymer block Q mainly composed of conjugated diene or isobutylene units, the block copolymer (I) having a weight average molecular weight of 30,000 to 200,000, a methacrylic resin (II) comprising 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith, and having an average degree of polymerization of 400 to 2,000, a methacrylic resin (III) comprising 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith, and having an average degree of polymerization of 6,000 to 40,000, and a softener (IV), the block copolymer (I) being mixed with a methacrylic resin (III) having an average degree of polymerization of 6,000 to 40,000, in a ratio of 0.1 to 1.0, and satisfying the following formulas (d), (e), and (f): 0.1≦W(II) / W(I)≦2.4 (d) 0.001≦W(III) / (W(I)+W(II))≦0.04 (e) 0≦W(IV) / (W(I)+W(II)+W(III)+W(IV))≦0.5 (f) (wherein W(I), W(II), W(III) and W(IV) respectively represent the contents (by mass) of the block copolymer (I), the methacrylic resin (II), the methacrylic resin (III) and the softener (IV) in the thermoplastic polymer composition), and the laminate has a layer (A) made of a cured resin and a layer (C) made of a pressure-sensitive adhesive, the layers being laminated in the order of (B)-(A)-(C). [Aspect 9] The laminate according to Aspect 8, wherein the thicknesses of the layer (A) made of the thermoplastic polymer composition, the layer (B) made of the cured resin, and the layer (C) made of the pressure-sensitive adhesive satisfy the following formulas (g) and (h): 0.02≦T(B) / T(A)≦0.30 (g) 0.04≦T(C) / (T(A)+T(B))≦0.50 (h) (where T(A), T(B), and T(C) represent the thicknesses (mm) of the layer (A) made of the thermoplastic polymer composition, the layer (B) made of the cured resin, and the layer (C) made of the pressure-sensitive adhesive, respectively. [Aspect 10] The laminate according to Aspect 8 or 9, wherein the thickness of the layer (A) made of the thermoplastic polymer composition is 100 to 300 μm.[Aspect 11] The laminate according to any one of Aspects 8 to 10, wherein the pressure-sensitive adhesive layer (C) contains an acrylic pressure-sensitive adhesive. [Aspect 12] The laminate according to Aspect 11, wherein the acrylic pressure-sensitive adhesive contains an acrylic block copolymer (V) having at least one polymer block R composed of structural units derived from a methacrylic acid ester and at least one polymer block S composed of structural units derived from an acrylic acid ester. [Aspect 13] The laminate according to Aspect 12, wherein the content of the acrylic block copolymer (V) in the pressure-sensitive adhesive layer (C) is 50% by mass or more. [Aspect 14] The laminate according to Aspect 12 or 13, wherein the content of the polymer block R in the acrylic block copolymer (V) is 10 to 50% by mass. [Aspect 15] The laminate according to Aspect 8, wherein the layer (C) made of the pressure-sensitive adhesive contains an aromatic vinyl block copolymer (VI) containing a polymer block containing 50% by mass or more of structural units derived from an aromatic vinyl monomer and a hydrogenated or non-hydrogenated polymer block containing 50% by mass or more of structural units derived from a conjugated diene monomer. [Aspect 16] The laminate of Aspect 15, wherein layer (C) made of the pressure-sensitive adhesive contains an aromatic vinyl block copolymer (VI), a tackifier resin (VII), and optionally a softener (VIII) in proportions that satisfy the following formulas (i) and (j): 0.1≦W(VII) / W(VI)≦3.0 (i) 0.0≦W(VIII) / (W(VI)+W(VII))≦1.0 (j) (where W(VI), W(VII), and W(VIII) represent the contents (by mass) of block copolymer (VI), tackifier resin (VII), and softener (VIII) in layer (C) made of the pressure-sensitive adhesive composite, respectively. [Aspect 17] The laminate of any one of Aspects 8 to 16, wherein layer (B) made of the cured resin contains a urethane (meth)acrylate resin. [Aspect 18] The laminate according to Aspect 17, wherein the urethane (meth)acrylate resin contains a fluorine atom and a silicon atom. [Aspect 19] A method for producing the laminate according to any one of Aspects 8 to 18, comprising laminating a layer (A) made of the thermoplastic polymer composition and a layer (C) made of a pressure-sensitive adhesive by melt co-extrusion. [Aspect 20] A protection film or protection sheet comprising the laminate according to any one of Aspects 8 to 18.

[0009] According to the present invention, a thermoplastic polymer composition can be provided that can be molded into a sheet or film that is highly transparent and exhibits low anisotropy, and that also has good sheet or film molding processability. Furthermore, by laminating a cured resin and a pressure-sensitive adhesive, the thermoplastic polymer composition of the present invention can provide a laminate that has high abrasion resistance and antifouling properties, as well as high adhesion to automotive steel plates and polar resin plates, low adhesive residue, and little change over time, and that can be coextruded. The laminate of the present invention can be suitably used as a protection film or protection sheet.

[0010] As used herein, the term "mainly composed of" means that the component, structural unit, etc., accounts for 50% by mass or more based on the total mass of the composition, polymer, etc.

[0011] The present invention provides a thermoplastic polymer composition comprising: a block copolymer (I) containing a polymer block P mainly composed of α-methylstyrene units and a hydrogenated or non-hydrogenated polymer block Q mainly composed of conjugated diene or isobutylene units, and having a weight-average molecular weight of 30,000 to 200,000; an acrylic resin (II) containing 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith, and having an average degree of polymerization of 400 to 2,000; an acrylic resin (III) containing 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith, and having an average degree of polymerization of 6,000 to 40,000; and a softener (IV). In a preferred embodiment, the thermoplastic polymer composition contains the block copolymer (I), acrylic resin (II), acrylic resin (III), and softener (IV) in proportions that satisfy the following formulae (a), (b), and (c): 0.1≦W(II) / W(I)≦2.4 (a) 0.001≦W(III) / (W(I)+W(II))≦0.04 (b) 0≦W(IV) / (W(I)+W(II)+W(III)+W(IV))≦0.5 (c) (wherein W(I), W(II), W(III), and W(IV) represent the contents (by mass) of the block copolymer (I), acrylic resin (II), acrylic resin (III), and softener (IV) in the thermoplastic polymer composition, respectively).

[0012] The reason why the effects of the present invention are achieved by adding specific amounts of an acrylic resin with a relatively low degree of polymerization and an acrylic resin with a relatively high degree of polymerization to a block copolymer containing a polymer block mainly composed of α-methylstyrene units is not clear, but is presumed to be as follows. It is generally known to be difficult to uniformly finely disperse an acrylic block copolymer in a styrene block copolymer. However, a styrene block copolymer containing a polymer block mainly composed of α-methylstyrene can uniformly retain an acrylic resin with relatively high fluidity (e.g., MFR of 10 g / 10 min or more (230°C, 37.3 N)) as an island structure in its continuous phase. If an acrylic resin with lower fluidity is present in the styrene block copolymer, the acrylic resin with lower fluidity is difficult to disperse in the continuous phase of the styrene block copolymer. Therefore, the acrylic resin is extruded from the continuous phase, and using the relatively high fluidity acrylic resin forming the fine island structure as a foothold, it forms a net-like structure that surrounds the island structure while more firmly maintaining it, thereby achieving the effects of the present invention.

[0013] Each component will be described below in order. In the following description, preferred specifications can be selected arbitrarily, and a combination of preferred specifications can be considered more preferred.

[0014] [Block Copolymer (I)] The block copolymer (I) used in the present invention is a block copolymer having a weight-average molecular weight of 30,000 to 200,000, comprising a polymer block P primarily composed of α-methylstyrene units and a hydrogenated or unhydrogenated polymer block Q primarily composed of conjugated diene compound units or isobutylene units. Compared to block copolymers or hydrogenated products thereof having a polymer block primarily composed of units other than α-methylstyrene units, such as styrene units, instead of the polymer block P, the use of block copolymer (I) significantly improves transparency, coatability, and mechanical properties. The total content of polymer block P and polymer block Q in block copolymer (I) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. This value does not take into account the presence of a coupling agent residue, as described below.

[0015] (Polymer Block P) The polymer block P constituting a part of the block copolymer (I) is mainly composed of α-methylstyrene units. As used herein, "mainly composed of" means that the polymer block P contains 50% by mass or more of α-methylstyrene units based on the total mass of the polymer block P. From the viewpoints of the transparency, coatability, and mechanical properties of the thermoplastic polymer composition, the content of α-methylstyrene units in the polymer block P is preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total mass of the polymer block P.

[0016] The polymer block P may contain other monomer units in an amount of 50% by mass or less, 30% by mass or less, 10% by mass or less, or 5% by mass or less, based on the total mass of the polymer block P, within a range that does not impair the object of the present invention. Examples of the other monomer include at least one selected from aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, and 4-(phenylbutyl)styrene; conjugated diene compounds such as butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene; and vinyl compounds such as isobutylene. When the polymer block P contains the other polymerizable monomer units, the configuration may be either random or tapered.

[0017] The weight-average molecular weight of the polymer block P is preferably 2,000 to 20,000, more preferably 3,000 to 15,000. When the weight-average molecular weight of the polymer block P is 2,000 or more, the compression set of the thermoplastic polymer composition at high temperatures is good, and when it is 20,000 or less, the melt viscosity of the block copolymer (I) does not become too high, and melt-mixing with other components is easy, resulting in excellent processability. Note that the weight-average molecular weight referred to in this specification is the molecular weight calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC).

[0018] The content of polymer block P in block copolymer (I) is preferably 5 to 70% by mass, more preferably 10 to 65% by mass, even more preferably 20 to 60% by mass, and particularly preferably 25 to 55% by mass, based on the total mass of polymer block P and polymer block Q. When the content of polymer block P is 5% by mass or more, the thermoplastic polymer composition exhibits good mechanical properties, good compression set at high temperatures, and excellent heat resistance. When the content is 70% by mass or less, the melt viscosity of block copolymer (I) does not become too high, facilitating melt-mixing with other components, and when formed into a thermoplastic polymer composition, exhibits excellent flexibility.

[0019] (Polymer Block Q) The polymer block Q constituting a part of the block copolymer (I) is mainly composed of conjugated diene compound units or isobutylene units, preferably mainly composed of conjugated diene compound units. As used herein, "mainly composed of" means that the polymer block Q contains 50% by mass or more of conjugated diene compound units or isobutylene units based on the total mass of the polymer block Q. The content of conjugated diene compound units or isobutylene units in the polymer block Q is preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total mass of the polymer block Q.

[0020] Examples of the conjugated diene compound forming the conjugated diene compound unit include at least one selected from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. Among these, butadiene, isoprene, or a mixture of butadiene and isoprene is preferred, and butadiene is more preferred. When the conjugated diene compound unit is composed of two or more types, the configuration may be any of random, block, and tapered.

[0021] Furthermore, the polymer block Q may be a hydrogenated product obtained by hydrogenating an unhydrogenated product (hereinafter, sometimes abbreviated as "hydrogenation"). Hydrogenation is preferred from the viewpoint of improving heat resistance, weather resistance, etc. The hydrogenation rate (hydrogenation rate) is not particularly limited, but preferably 70 mol % or more of the carbon-carbon double bonds based on the conjugated diene compound units in all polymer blocks Q are hydrogenated, more preferably 80 mol % or more, more preferably 85 mol % or more, even more preferably 90 mol % or more, and particularly preferably 95 mol % or more. The hydrogenation rate of the carbon-carbon double bonds in the polymer block Q can be determined by nuclear magnetic resonance spectroscopy ( １ H-NMR spectrum), and the same applies hereinafter.

[0022] Furthermore, polymer block Q may contain units of other polymerizable monomers other than conjugated diene compound units and isobutylene units, provided that the content of these units is 50% by mass or less, 30% by mass or less, 10% by mass or less, or 5% by mass or less, based on the total mass of polymer block Q, within a range that does not impair the object of the present invention. Examples of such monomers include at least one aromatic vinyl compound selected from styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, etc. When polymer block Q contains a monomer other than conjugated diene compound units and isobutylene units, the polymer block may have either a random or tapered configuration.

[0023] The content of polymer block Q in block copolymer (I) is preferably 30 to 95% by mass, more preferably 35 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 45 to 75% by mass, based on the total mass of polymer blocks P and Q. If the content of polymer block Q is 30% by mass or more, the melt viscosity of block copolymer (I) does not become too high, facilitating melt-mixing with other components. On the other hand, if the content of polymer block Q is 95% by mass or less, the resulting thermoplastic polymer composition exhibits excellent compression set at high temperatures. The weight-average molecular weight (Mw) of polymer block Q is preferably 9,000 to 190,000. If the weight-average molecular weight of polymer block Q is 9,000 or more, the thermoplastic polymer composition exhibits good heat resistance. If the weight-average molecular weight is 190,000 or less, the melt viscosity of block copolymer (I) does not become too high, facilitating blending with other components, resulting in excellent processability.

[0024] (Bonding Mode Between Polymer Block P and Polymer Block Q) The bonding mode between polymer block P and polymer block Q in block copolymer (I) may be linear, branched, radial, or any combination thereof. Among these, linear, branched, or a combination thereof is preferred. For example, when polymer block P is represented by P and polymer block Q is represented by Q, examples include P-Q diblock copolymers, P-Q-P triblock copolymers, P-Q-P-Q tetrablock copolymers, and (P-Q)nX copolymers (X represents a coupling agent residue, and n represents an integer of 3 or more). Block copolymers having these bonding modes can be used alone or in combination of two or more. Among these, P-Q-P triblock copolymers or a mixture of P-Q-P triblock copolymers and P-Q diblock copolymers are preferred as block copolymer (I).

[0025] Here, in the present specification, when polymer blocks of the same type are linearly bonded via a divalent coupling agent or the like, the entire bonded polymer blocks are treated as a single polymer block. Accordingly, polymer blocks that should strictly be expressed as Y-X-Y (X represents a coupling agent residue), including the above examples, are expressed as Y as a whole, unless there is a particular need to distinguish them from a single polymer block Y. In the present specification, since this type of polymer block containing a coupling agent residue is treated as above, for example, a block copolymer containing a coupling agent residue and that should strictly be expressed as Y-Z-X-Z-Y (X represents a coupling agent residue) is expressed as Y-Z-Y and is treated as an example of a triblock copolymer.

[0026] Furthermore, within the scope of the present invention, the block copolymer (I) may contain a polymer block R composed of a polymerizable monomer other than α-methylstyrene, a conjugated diene compound, and isobutylene, such as methyl methacrylate, styrene, etc. In this case, when the polymer block R is represented by R, examples of the structure of the block copolymer include a P-QR triblock copolymer, a P-Q-R-P tetrablock copolymer, and a P-Q-P-R tetrablock copolymer.

[0027] (Properties of Block Copolymer (I)) In the thermoplastic polymer composition of the present invention, the weight-average molecular weight of the block copolymer (I) is 30,000 to 200,000. If the weight-average molecular weight is within this range, the resulting thermoplastic polymer composition can be excellent in all of transparency, ease of application, and mechanical properties. From this viewpoint, the weight-average molecular weight of the block copolymer (I) is preferably 40,000 to 150,000, more preferably 40,000 to 100,000. The structure of the block copolymer (I) is not limited to being linear, branched, or the like.

[0028] There is no particular limitation on the method for producing the block copolymer (I). In the present invention, known block copolymers (I) can also be used without particular limitation. For example, the Septon (registered trademark) Q series manufactured by Kuraray Co., Ltd. can be mentioned.

[0029] [Acrylic Resin (II)] The acrylic resin (II) used in the present invention contains 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith, and has an average degree of polymerization of 400 to 2,000. Typically, the average degree of polymerization can be determined by dissolving the resin in a solvent and converting the resulting viscosity. The content of methyl methacrylate units in the acrylic resin (II) is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. It may be 90% by mass or more, or it may be 100% by mass, i.e., composed solely of methyl methacrylate units.

[0030] Examples of copolymerizable vinyl monomers include olefin compounds such as ethylene and propylene; acrylic acid or metal salts thereof; acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate; methacrylic acid or metal salts thereof; methacrylic acid esters such as ethyl methacrylate, n-butyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, and cyclohexyl methacrylate; vinyl acetate; aromatic vinyl compounds such as styrene, α-methylstyrene, and p-methylstyrene; maleic anhydride; and maleimide compounds such as N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. When these are copolymerized with methyl methacrylate, one type may be used alone, or two or more types may be used in combination. In a copolymer obtained by copolymerizing methyl methacrylate with another copolymerizable vinyl monomer, the ratio of the other copolymerizable vinyl monomer is preferably a ratio that does not significantly change the properties of the acrylic resin (II), specifically, 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less. As the acrylic resin (II), a combination of at least one selected from ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate copolymer (EBA) with polymethyl methacrylate (PMMA) is also preferred. As a copolymer to be used in combination with PMMA, EMA is more preferred from the viewpoint of facilitating viscosity adjustment of the thermoplastic polymer composition.

[0031] The average degree of polymerization of the acrylic resin (II) is 400 to 2,000, preferably 800 to 1,200. If the average degree of polymerization is higher than this, the viscosity of the composition after blending increases, making melt extrusion difficult, and it becomes difficult to finely disperse the acrylic resin (II) during blending, resulting in reduced transparency. If the average degree of polymerization is lower than this, drawdown is more likely to occur, making melt extrusion difficult. The melt flow rate of the acrylic resin (II), measured in accordance with ISO 1133-1:2011 under conditions of 230°C and 37.3N, is preferably 5 to 25 g / 10 min, more preferably 5 to 20 g / 10 min, and even more preferably 5 to 15 g / 10 min. If the melt flow rate is outside this range, the fluidity of the composition fluctuates, making it difficult to mold it into a sheet or film shape.

[0032] The acrylic resin (II) can be produced by a general polymerization method such as solution polymerization, emulsion polymerization, or suspension polymerization, and the production method is not particularly limited. In the present invention, known acrylic resins (II) can also be used without any particular limitation. Examples include the ACRYPET (registered trademark) series manufactured by Mitsubishi Rayon Co., Ltd., the DELPET (registered trademark) series manufactured by Asahi Kasei Chemicals Corporation, the SUMIPEX (registered trademark) series manufactured by Sumitomo Chemical Co., Ltd., and the PARAPET (registered trademark) series manufactured by Kuraray Co., Ltd.

[0033] [Acrylic Resin (III)] The acrylic resin (III) used in the present invention contains 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith, and has an average degree of polymerization of 6,000 to 40,000. The content of methyl methacrylate units in the acrylic resin (III) is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. It may be 90% by mass or more, or it may be 100% by mass, i.e., it may be composed of only methyl methacrylate units.

[0034] Examples of copolymerizable vinyl monomers include olefin compounds such as ethylene and propylene; acrylic acid or metal salts thereof; acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate; methacrylic acid or metal salts thereof; methacrylic acid esters such as ethyl methacrylate, n-butyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, and cyclohexyl methacrylate; vinyl acetate; aromatic vinyl compounds such as styrene, α-methylstyrene, and p-methylstyrene; maleic anhydride; and maleimide compounds such as N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. When these are copolymerized with methyl methacrylate, one type may be used alone, or two or more types may be used in combination. In a copolymer obtained by copolymerizing methyl methacrylate with another copolymerizable vinyl monomer, the ratio of the other copolymerizable vinyl monomer is preferably a ratio that does not significantly change the properties of the acrylic resin (III), specifically 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less. As the acrylic resin (III), a combination of at least one selected from ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate copolymer (EBA) with polymethyl methacrylate (PMMA) is also preferred.

[0035] The average degree of polymerization of the acrylic resin (III) is 6,000 to 40,000, preferably 8,000 to 36,000, and more preferably 10,000 to 32,000. If the average degree of polymerization is lower than this, it may become difficult for the acrylic resin (III) to form a net-like structure independently from the acrylic resin (II), and not only does the transparency of the film decrease, but sufficient improvements in film forming processability (film thickness stability, high melt tension, good spreadability) are not observed. On the other hand, if the average degree of polymerization of the acrylic resin (III) is higher than this, it may become difficult for the acrylic resin (III) to disperse during blending, and not only does the transparency of the film decrease, but sufficient improvements in film forming processability (film thickness stability, high melt tension, good spreadability) are not observed.

[0036] The acrylic resin (III) can be produced by a general polymerization method such as solution polymerization, emulsion polymerization, or suspension polymerization, and the production method is not particularly limited. In the present invention, known acrylic resins (III) can also be used without particular limitation. Examples include the Metablen (registered trademark) P series manufactured by Mitsubishi Chemical Corporation and the Kane Ace (registered trademark) PA series manufactured by Kaneka Corporation.

[0037] [Softener (IV)] The softener (IV) used in the present invention may be any known softener, such as a hydrocarbon oil such as paraffinic, naphthenic, or aromatic; vegetable oil such as peanut oil or rosin; phosphate ester; low-molecular-weight polyethylene glycol; liquid paraffin; or a hydrocarbon synthetic oil such as low-molecular-weight polyethylene, ethylene-α-olefin copolymer oligomer, liquid polybutene, liquid polyisoprene or its hydrogenated product, or liquid polybutadiene or its hydrogenated product. These may be used alone or in combination of two or more. Of these, paraffinic hydrocarbon oils and hydrocarbon synthetic oils such as ethylene-α-olefin copolymer oligomer are preferred. The kinematic viscosity of the softener (IV) at 40°C is preferably 50 to 1,000 mm from the viewpoints of moldability and ease of application. ２ / s, more preferably 50 to 800 mm ２ / s, more preferably 80 to 600 mm ２ / s.

[0038] (Contents of Block Copolymer (I), Acrylic Resin (II), Acrylic Resin (III), and Softener (IV)) In a preferred embodiment of the thermoplastic polymer composition of the present invention, the block copolymer (I), the acrylic resin (II), the acrylic resin (III), and the softener (IV) are represented by the following formulas (a), (b), and (c): 0.1≦W(II) / W(I)≦2.4 (a) 0.001≦W(III) / (W(I)+W(II))≦0.04 (b) 0≦W(IV) / (W(I)+W(II)+W(III)+W(IV))≦0.5 (c) (wherein W(I), W(II), W(III), and W(IV) represent the contents (by mass) of the block copolymer (I), the acrylic resin (II), the acrylic resin (III), and the softener (IV) in the thermoplastic polymer composition, respectively). It contains in a proportion that satisfies the following.

[0039] In formula (a), if the value of "W(II) / W(I)", i.e., the ratio (mass ratio) of the content of the acrylic resin (II) to the block copolymer (I) in the thermoplastic polymer composition, is less than 0.1, the ease of application and mechanical properties will be insufficient, and if it exceeds 2.4, the flexibility, rubber elasticity, transparency, and mechanical properties of the thermoplastic polymer composition will be poor. The value of "W(II) / W(I)" is preferably 0.2 to 2.0, more preferably 0.3 to 1.8, even more preferably 0.4 to 1.6, and particularly preferably 0.6 to 1.3.

[0040] Furthermore, in formula (b), if the value of "W(III) / (W(I)+W(II))" (i.e., the ratio (mass ratio) of the content of the acrylic resin (III) to the total content of the block copolymer (I) and the acrylic resin (II)) is less than 0.001, the film formability will not be sufficiently improved. Furthermore, if it exceeds 0.04, the transparency of the composition may decrease, or the melt tension may become too high, making both ends of the melt curtain more likely to tear during molding. The value of "W(III) / (W(I)+W(II))" is preferably 0.005 to 0.04, more preferably 0.008 to 0.04, even more preferably 0.009 to 0.04, even more preferably 0.009 to 0.035, even more preferably 0.009 to 0.02, and particularly preferably 0.009 to 0.015.

[0041] In formula (c), when the value of "W(IV) / (W(I)+W(II)+W(III)+W(IV))", i.e., the ratio (mass ratio) of the content of the softener (IV) to the total content of the block copolymer (I), the acrylic resin (II), the acrylic resin (III), and the softener (IV), exceeds 0.5, the coatability and mechanical properties become poor. The lower limit of "W(IV) / (W(I)+W(II)+W(III)+W(IV))" is 0, and the softener (IV) does not need to be contained. However, from the viewpoints of transparency, coatability, and moldability, it is preferable that the softener (IV) be contained. The value of "W(IV) / (W(I)+W(II)+W(III)+W(IV))" is preferably 0.01 to 0.5, more preferably 0.01 to 0.3, and even more preferably 0.03 to 0.2.

[0042] [Other Components] The thermoplastic polymer composition of the present invention may contain other thermoplastic polymers different from the block copolymer (I), the acrylic resin (II), and the acrylic resin (III), as needed. Other thermoplastic polymers include, for example, polyethylenes such as medium-density polyethylene and low-density polyethylene (LDPE); ethylene-α-olefin copolymers such as ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-heptene copolymer, ethylene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-nonene copolymer, and ethylene-1-decene copolymer; ethylene-vinyl acetate copolymer; polypropylenes such as atactic polypropylene, isotactic polypropylene, and syndiotactic polypropylene; polyolefin resins such as ethylene-propylene random copolymers and ethylene-vinyl acetate copolymers; styrene resins such as polystyrene, poly(α-methylstyrene), and styrene-acrylonitrile copolymer; styrene block copolymers having styrene blocks as hard segments, different from the block copolymer (I); polyphenylene oxide, polycarbonate, thermoplastic polyolefin elastomers, and crosslinked thermoplastic polyolefin elastomers. These may be used alone or in combination of two or more. Among these, polyethylene and polypropylene are preferred, and polypropylene is more preferred. The melt flow rates of the polyethylene and polypropylene are preferably 5 to 60 g / 10 min, more preferably 10 to 60 g / 10 min. When other thermoplastic polymers are contained, the content thereof is preferably 60% by mass or less, more preferably 50% by mass or less, based on the thermoplastic polymer composition.

[0043] Furthermore, the total content of the block copolymer (I), the acrylic resin (II), the acrylic resin (III), and the softener (IV) in the thermoplastic resin composition of the present invention is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 70% by mass or more, and may be 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass.

[0044] Furthermore, the thermoplastic polymer composition of the present invention may contain components other than those described above. Examples of such components include inorganic fillers such as talc, clay, mica, calcium silicate, glass, hollow glass spheres, glass fiber, calcium carbonate, magnesium carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc borate, dawsonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, graphite, carbon fiber, activated carbon, hollow carbon spheres, calcium titanate, lead zirconate titanate, silicon carbide, and mica; organic fillers such as wood flour and starch; and organic pigments. Furthermore, the composition may further contain a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antioxidant, a lubricant, a colorant, an antistatic agent, a flame retardant, a foaming agent, a water repellent, a waterproofing agent, a tackifying resin, an electrical conductivity imparting agent, a thermal conductivity imparting agent, an electromagnetic wave shielding agent, a fluorescent agent, an antiblocking agent, or an antibacterial agent, as necessary.

[0045] When the thermoplastic polymer composition of the present invention contains the other components (excluding the "other thermoplastic polymers"), there are no particular restrictions on the content thereof as long as the effects of the present invention are not significantly impaired. In general, the content of each of the other components is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the total amount of the components (I) to (IV).

[0046] (Characteristics and Physical Properties of Thermoplastic Polymer Composition) The Shore A hardness of the thermoplastic polymer composition of the present invention, measured at 23°C using a 2 mm thick press sheet in accordance with JIS K 6253-3:2023, is preferably about 30 to 100. The specific gravity, measured by Method A in accordance with JIS K 7112-1:2023 using a 2 mm thick press sheet, is preferably 0.9 to 1.10 g / cm ３ The melt flow rate (MFR) of the resin, measured by Method A in accordance with JIS K 7210-1:2014 under conditions of 230°C and 21.2N, is preferably about 0.5 to 40 g / 10 min, and more preferably in the range of 0.5 to 35 g / 10 min. When the MFR is in this range, the flowability and moldability are good.

[0047] When the thermoplastic polymer composition of the present invention is molded into a film having a thickness of 150 μm using an extruder, the difference between the maximum and minimum film thicknesses (film thickness variation) determined by the method described in the Examples is preferably 25 μm or less, more preferably 20 μm or less, even more preferably 17 μm or less, and even more preferably 15 μm or less.

[0048] Furthermore, a film having a thickness of 150 μm formed by an extruder using the thermoplastic polymer composition of the present invention has a film thickness variation coefficient, which is expressed as the ratio of film thickness variation to the average film thickness (actually measured value), of 5% or less, preferably 4% or less, more preferably 3% or less, and even more preferably 2% or less. The film thickness variation coefficient can be calculated using the following formula: (film thickness variation coefficient) [%] = (film thickness variation) / (average film thickness) × 100.

[0049] Furthermore, the thermoplastic polymer composition of the present invention has a strand breakage tension of preferably 30 kPa or more, more preferably 40 kPa or more, and even more preferably 50 kPa or more, when extruded at an extrusion temperature of 230°C through a capillary having a diameter of 1 mm and a length of 10 mm at a piston speed of 5 mm / min using a melt tension measurement device of a capillary rheometer and withdrawn. The strand breakage speed under the same conditions is preferably 40 m / min or more, more preferably 50 m / min or more, and even more preferably 60 m / min or more. The tensile strength of the thermoplastic polymer composition of the present invention, measured in accordance with JIS K 6251:2023 using a dumbbell No. 3 and a pulling speed of 500 mm / min, is preferably 10 to 60 MPa, more preferably 15 to 60 MPa, and even more preferably 20 to 60 MPa. The breaking elongation under the same conditions is preferably about 180 to 500%.

[0050] Furthermore, the thermoplastic polymer composition of the present invention has a haze value of preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.2 or less, and even more preferably 0.9 or less, measured in accordance with JIS K7136:2000 using a film formed to a thickness of 150 μm using an extruder. In other words, a molded article obtained using the thermoplastic polymer composition of the present invention has excellent transparency. The thermoplastic polymer composition of the present invention has a tear strength in the MD direction and a tear strength in the TD direction, measured in accordance with JIS K6252-1:2015 at 23°C using an unnotched angle-shaped test specimen, and the tear strength is preferably 400 N / cm or more, more preferably 430 N / cm or more, and even more preferably 450 N / cm or more, using a film formed to a thickness of 150 μm using an extruder. Furthermore, the tear strength in the MD direction and the tear strength in the TD direction are each preferably 400 N / cm or more, more preferably 450 N / cm or more, and even more preferably 500 N / cm or more, and can also be 550 N / cm or more, and 600 N / cm or more.

[0051] (Method for producing thermoplastic polymer composition) The thermoplastic polymer composition of the present invention is not particularly limited, and can be produced, for example, by the following method. Specifically, all components to be mixed are first melt-kneaded by a known method to produce pellets. For example, pellets of the thermoplastic polymer composition are obtained by melt-kneading the components using a kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a Brabender mixer, an open roll, or a kneader. The kneading temperature is generally preferably 160 to 280°C, and more preferably 190 to 260°C.

[0052] The melt-kneading may be carried out in the following manner: (1) all components constituting the thermoplastic polymer composition are dry-blended in advance using a mixer such as a high-speed mixer or a tumbler mixer before being kneaded, and then all components are melt-kneaded at once; (2) components other than the softener (IV) are first fed into an extruder to start melt-kneading, and a predetermined amount of the softener (IV) is added to the extruder halfway through the process using a side feeder or the like, and then all components are melt-kneaded; or (3) components other than the acrylic resin (II) are melt-kneaded in advance, and then a predetermined amount of the acrylic polymer (II) is added to the extruder halfway through the process using a side feeder or the like, and then all components are melt-kneaded.

[0053] The thermoplastic polymer composition thus obtained can be molded and processed by various molding methods, such as injection molding (insert molding, two-color molding, sandwich molding, gas injection molding, etc.), extrusion molding, inflation molding, T-die film molding, lamination molding, blow molding, hollow molding, compression molding, and calendar molding.

[0054] The thermoplastic polymer composition of the present invention can be used for, for example, automobile interior and exterior material parts such as instrument panels, rack and opinion boots, suspension boots, constant velocity joint boots, bumpers, side moldings, weather strips, mudguards, emblems, leather seats, floor mats, armrests, airbag covers, steering wheel coverings, belt line moldings, flush mounts, gears, knobs, etc.; hoses and tubes such as pressure hoses, fire hoses, painting hoses, washing machine hoses, fuel tubes, oil and air pressure tubes, and dialysis tubes; grip materials for various products (for example, scissors, screwdrivers, toothbrushes, pens, cameras, etc.); home appliance parts such as refrigerator gaskets, vacuum cleaner bumpers, mobile phone protective films, and waterproof bodies; copier feed rollers, winding the same can be effectively used in a wide range of applications, including office machine parts such as cleaning rollers; furniture such as sofas and chair seats; parts such as switch covers, casters, stoppers, and foot rubbers; building materials such as coated steel plates and coated plywood; sporting goods such as swimming goggles, snorkels, ski poles, ski boots, snowboard boots, ski and snowboard covering materials, golf ball covers, various types of shoes, and shoe outer soles; medical supplies such as syringe gaskets and rolling tubes; industrial materials such as conveyor belts, electric belts, and pelletizer rolls; elastic parts for sanitary materials such as disposable diapers, poultices, and bands such as hair bands, wristbands, watch bands, and eyeglass bands; snow chains, electric wire covering materials, trays, films, sheets, stationery, toys, and daily commodities.

[0055] The present invention also encompasses a sheet or film made of the thermoplastic polymer composition. Although there is generally no clear distinction between a sheet and a film, a film having a thickness of 200 μm or less tends to be called a film, and a sheet having a thickness greater than that tends to be called a sheet, and the same applies to the present invention.

[0056] From the viewpoints of transparency, ease of application, and mechanical properties, the method for producing a sheet or film preferably includes a molding step using a film molding machine containing a static mixer. More specifically, the film molding machine is arranged so that a static mixer is connected continuously to the outlet of a kneader similar to the single-screw extruder, twin-screw extruder, Banbury mixer, Brabender, open roll, kneader, etc., used when melt-kneading all the components constituting the thermoplastic polymer composition of the present invention to produce pellets, and film molding is performed by placing the film molding machine, and in this case, it is preferable that the static mixer is placed before the T-die. Note that the pellet production step may be omitted and film molding may be performed directly by melt-kneading.

[0057] In forming a film or sheet, from the viewpoint of enhancing transparency, the cylinder temperature in the static mixer is preferably 180 to 270°C, more preferably 190 to 260°C, and even more preferably 200 to 250°C. The die head temperature is preferably 210 to 270°C, more preferably 220 to 260°C. The screw speed is preferably 20 to 70 rpm, more preferably 20 to 60 rpm. The cast roll temperature is preferably 10 to 110°C, more preferably 20 to 100°C.

[0058] To obtain transparency and mechanical properties, it is preferable to produce a sheet or film by passing the sheet or film-like resin extruded from a T-die through the gap between at least one pair of pressure rolls while applying pressure. It is even more preferable that at least one of the pair of pressure rolls is a metal elastic roll. Furthermore, from the viewpoints of suppressing the inclusion of foreign matter and fisheyes, as well as transparency, it is preferable that a screen mesh be included in the film molding machine. While there are no particular restrictions on the mesh count of the screen mesh, from the viewpoints of suppressing the inclusion of foreign matter and fisheyes, it is preferably 40 mesh or more, more preferably 60 mesh or more, and even more preferably 70 mesh or more. From the viewpoint of achieving transparency, it is preferably 300 mesh or less, more preferably 250 mesh or less, and even more preferably 150 mesh or less. Therefore, the mesh count of the screen mesh is preferably 40 to 300 mesh, more preferably 60 to 250 mesh, and even more preferably 70 to 150 mesh. The transparency can be further enhanced by suppressing the expansion of dispersed particles in the resin due to shear stress when the molten resin passes through the screen mesh. In this specification, the mesh number means the number of meshes per inch (25.4 mm) as specified by ASTM E11.

[0059] The upper limit of the thickness of the sheet or film is preferably 800 μm, more preferably 600 μm, even more preferably 400 μm, and particularly preferably 300 μm, and the lower limit of the thickness of the sheet or film is preferably 10 μm, more preferably 30 μm, even more preferably 50 μm, and particularly preferably 80 μm.

[0060] [Laminate] The present invention also includes a laminate having a layer (A) made of the thermoplastic polymer composition, a layer (B) made of a cured resin, and a layer (C) made of a pressure-sensitive adhesive, which are laminated in the order of (B)-(A)-(C).

[0061] [Layer (A) Made of Thermoplastic Polymer Composition] (Contents of Block Copolymer (I), Acrylic Resin (II), Acrylic Resin (III), and Softener (IV)) The thermoplastic polymer composition contained in the layer (A) made of a thermoplastic polymer composition in the laminate of the present invention (hereinafter, may be referred to as thermoplastic polymer composition layer (A)) is a layer in which the block copolymer (I), the acrylic resin (II), the acrylic resin (III), and the softener (IV) are represented by the following formulas (d), (e), and (f): 0.1≦W(II) / W(I)≦2.4 (d) 0.001≦W(III) / (W(I)+W(II))≦0.04 (e) 0≦W(IV) / (W(I)+W(II)+W(III)+W(IV))≦0.5 (f) [wherein W(I), W(II), W(III), and W(IV) represent the contents (by mass) of the block copolymer (I), acrylic resin (II), acrylic resin (III), and softener (IV) in the thermoplastic polymer composition, respectively.] The preferred ranges of formulas (d) to (f) are the same as the preferred ranges of formulas (a) to (c).

[0062] A preferred embodiment of the laminate of the present invention is a layer (A) made of a thermoplastic resin composition having a film thickness variation coefficient of 5% or less, measured according to JIS K 7130: 1999 using a film molded to a thickness of 150 μm using an extruder, and having tear strengths of 400 N / cm or more in both the MD and TD directions at room temperature, measured using an unnotched angle-shaped test piece according to JIS K 6252-1: 2015. Furthermore, the laminate of the present invention preferably has tear strengths of 400 N / cm or more in both the MD and TD directions, measured using an unnotched angle-shaped test piece according to JIS K 6252-1: 2015.

[0063] [Layer (B) made of cured resin] The layer (B) made of cured resin in the laminate of the present invention (hereinafter sometimes referred to as cured resin layer (B)) can be made of any cured resin without any particular limitation, and any curing method can be used. In view of adhesion to the thermoplastic polymer composition layer (A), the cured resin layer (B) is preferably made of a urethane (meth)acrylate resin. In view of antifouling properties, the urethane (meth)acrylate resin preferably contains a fluorine atom and a silicon atom.

[0064] [Layer (C) made of pressure-sensitive adhesive] The layer (C) made of pressure-sensitive adhesive (hereinafter sometimes referred to as pressure-sensitive adhesive layer (C)) in the laminate of the present invention can be one or more pressure-sensitive adhesives selected from the group consisting of pressure-sensitive adhesives such as synthetic rubber-based pressure-sensitive adhesives, acrylic-based pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, etc., without any particular limitation. In view of the adhesiveness to the thermoplastic polymer composition layer (A), the pressure-sensitive adhesive layer (C) is preferably one containing an acrylic pressure-sensitive adhesive or a synthetic rubber pressure-sensitive adhesive.

[0065] [Acrylic Pressure-Sensitive Adhesive] The pressure-sensitive adhesive layer (C) preferably contains, as the acrylic pressure-sensitive adhesive, an acrylic block copolymer (V) having at least one polymer block R composed of structural units derived from a methacrylic acid ester and at least one polymer block S composed of structural units derived from an acrylic acid ester. The content of the acrylic block copolymer (V) in the pressure-sensitive adhesive layer (C) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0066] The acrylic pressure-sensitive adhesive may contain an acrylic polymer other than the acrylic block copolymer (V). Examples of acrylic polymers other than the acrylic block copolymer (V) include (meth)acrylic acid ester homopolymers such as polymethyl methacrylate, random copolymers of (meth)acrylic acid esters, ethylene-acrylic acid ester copolymers, ethylene-methacrylic acid copolymers (EMAA resins), AS resins, ABS resins, AES resins, AAS resins, ACS resins, MBS resins, and styrene-methyl methacrylate copolymers, but are not particularly limited thereto and include polymers obtained by using (meth)acrylic acid or a (meth)acrylic acid ester as at least one of the raw materials.

[0067] The weight-average molecular weight (Mw) of the acrylic block copolymer (V) is usually preferably 30,000 to 300,000, and more preferably 45,000 to 150,000. When the Mw of the acrylic block copolymer (V) is 30,000 or more, the melt viscosity of the acrylic block copolymer (V) does not become extremely small, improving take-up properties with a roll and facilitating coextrusion molding. When the Mw of the acrylic block copolymer (V) is 300,000 or less, the melt viscosity of the acrylic block copolymer (V) does not become extremely large, reducing the risk of surface roughness of the molded article obtained by coextrusion molding. From the viewpoint of adhesive properties such as improving the cohesive strength of the pressure-sensitive adhesive layer (C), the ratio of Mw to Mn (Mw / Mn) of the acrylic block copolymer (V) is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, even more preferably 1.0 to 1.5, and particularly preferably 1.0 to 1.3.

[0068] Examples of the methacrylate esters that are constituent units of the polymer block R include methacrylates that do not have a functional group, such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, isobornyl methacrylate, phenyl methacrylate, and benzyl methacrylate; and methacrylates that have a functional group, such as methoxyethyl methacrylate, ethoxyethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, glycidyl methacrylate, and tetrahydrofurfuryl methacrylate.

[0069] Among these, from the viewpoint of improving the transparency, heat resistance, and durability of the acrylic pressure-sensitive adhesive, methacrylic acid esters having no functional group are preferred, with methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and phenyl methacrylate being more preferred, and methyl methacrylate being even more preferred. The polymer block R may be composed of one or more of these methacrylic acid esters. Furthermore, from the viewpoint of improving durability, it is preferable that the acrylic block copolymer (V) contains two or more polymer blocks R. In this case, the polymer blocks R may be the same or different.

[0070] The weight-average molecular weight (Mw) of the polymer block R is not particularly limited, but is typically preferably 1,000 to 50,000, and more preferably 4,000 to 20,000. When the weight-average molecular weight (Mw) of the polymer block R is 1,000 or more, the resulting acrylic block copolymer (V) or an acrylic pressure-sensitive adhesive containing the acrylic block copolymer (V) is less likely to have insufficient cohesive strength. Furthermore, when the weight-average molecular weight (Mw) of the polymer block R is 50,000 or less, the melt viscosity of the resulting acrylic pressure-sensitive adhesive is not too high, resulting in good productivity and coextrusion moldability of the acrylic block copolymer (V). The proportion of methacrylic acid ester units contained in the polymer block R is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the polymer block R.

[0071] The content of polymer block R in the acrylic block copolymer (V) is preferably 10 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass, in order to provide excellent adhesive properties and enable the supply of the acrylic block copolymer (V) or an acrylic pressure-sensitive adhesive containing the acrylic block copolymer (V) in a form that is easy to handle (for example, pellets).

[0072] Examples of the acrylic acid ester units constituting the polymer block S include acrylic acid esters without functional groups, such as n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, lauryl acrylate, phenyl acrylate, and benzyl acrylate; and acrylic acid esters with functional groups, such as methoxyethyl acrylate, ethoxyethyl acrylate, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-aminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, and phenoxyethyl acrylate. Among these, acrylic acid esters without functional groups are preferred from the viewpoint of improving the transparency, flexibility, cold resistance, and low-temperature properties of the resulting acrylic pressure-sensitive adhesive containing the acrylic block copolymer (V). These may be used alone or in combination of two or more.

[0073] When the acrylic block copolymer (V) contains two or more polymer blocks S, the polymer blocks S may have the same or different structures. The proportion of acrylic acid ester units contained in the polymer block S is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, of the polymer block S.

[0074] The polymer block R and the polymer block S may contain components of each other to the extent that the effects of the present invention are not impaired. When the components of each other are contained, the structure may be a random structure, or a gradient structure (tapered structure) in which the copolymerization ratio gradually changes at one or more boundaries between the polymer block R and the polymer block S. Furthermore, other monomers may be contained as necessary. Examples of such other monomers include vinyl compounds having a carboxyl group such as (meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, and fumaric acid; vinyl monomers having a functional group such as (meth)acrylamide, (meth)acrylonitrile, vinyl acetate, vinyl chloride, and vinylidene chloride; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and m-methylstyrene; conjugated diene compounds such as butadiene and isoprene; olefin compounds such as ethylene, propylene, isobutene, and octene; and lactone monomers such as ε-caprolactone and valerolactone. When these are contained, the amount thereof is usually preferably 40% by mass or less, more preferably 20% by mass or less, based on the total mass of the monomers used in each polymer block.

[0075] The acrylic block copolymer (V) may contain other polymer blocks, if necessary, in addition to the polymer block R and polymer block S. Examples of such other polymer blocks include polymer or copolymer blocks composed of styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, isobutene, butadiene, isoprene, octene, vinyl acetate, maleic anhydride, vinyl chloride, vinylidene chloride, etc.; polymer blocks composed of polyethylene terephthalate, polylactic acid, polyurethane, polydimethylsiloxane, etc. The polymer blocks also include hydrogenated products of polymer blocks containing conjugated diene compounds such as butadiene and isoprene.

[0076] The method for producing the acrylic block copolymer (V) is not particularly limited, and a method based on a known method can be used. Alternatively, commercially available products such as the Kuralyte (registered trademark) series manufactured by Kuraray Co., Ltd. can also be used.

[0077] The acrylic pressure-sensitive adhesive may further contain one or more additives such as a tackifying resin, a softener, a plasticizer, a heat stabilizer, a light stabilizer, an antistatic agent, a flame retardant, a foaming agent, a colorant, a dye, a refractive index adjuster, a filler, or a curing agent, provided that the effects of the present invention are not impaired.

[0078] Examples of the tackifying resin include, from the viewpoint of facilitating adjustment of tack, adhesive strength, and holding power, rosins such as gum rosin, tall oil rosin, and wood rosin; modified rosins such as hydrogenated rosin, disproportionated rosin, and polymerized rosin; rosin-based resins such as rosin esters of these rosins and modified rosins, such as glycerin esters and pentaerythritol esters; terpene-based resins such as terpene resins based on α-pinene, β-pinene, dipentene, etc., aromatic modified terpene resins, hydrogenated terpene resins, and terpene phenol resins; (hydrogenated) aliphatic (C5) petroleum resins, (hydrogenated (Hydrogenated) petroleum resins such as aromatic (C9) petroleum resins, (hydrogenated) copolymer (C5 / C9) petroleum resins, (hydrogenated) dicyclopentadiene petroleum resins, and alicyclic saturated hydrocarbon resins; styrene polymers such as poly-α-methylstyrene, α-methylstyrene / styrene copolymers, styrene monomer / aliphatic monomer copolymers, styrene monomer / α-methylstyrene / aliphatic monomer copolymers, styrene monomer copolymers, and styrene monomer / aromatic monomer copolymers; and synthetic resins such as coumarone-indene resins, phenolic resins, and xylene resins. Among the above tackifying resins, rosin resins, terpene resins, (hydrogenated) petroleum resins, and styrene resins are preferred in terms of exhibiting high adhesive strength. These may be used alone or in combination of two or more.

[0079] Furthermore, when a tackifier resin is contained, the content thereof is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, even more preferably 5 to 50 parts by mass, particularly preferably 5 to 40 parts by mass, and most preferably 5 to 35 parts by mass, relative to 100 parts by mass of the acrylic block copolymer (V), from the viewpoints of adhesive strength and durability.

[0080] As the styrene-based resin, commercially available products such as sx100 (manufactured by Yasuhara Chemical Co., Ltd.), FTR6000 series, and FTR7000 series (manufactured by Mitsui Chemicals, Inc.) can be used.

[0081] Examples of the softening agent or plasticizer include fatty acid esters such as dibutyl phthalate, di-n-octyl phthalate, bis-2-ethylhexyl phthalate, di-n-decyl phthalate, and diisodecyl phthalate; adipate esters such as bis-2-ethylhexyl adipate and di-n-octyl adipate; sebacate esters such as bis-2-ethylhexyl sebacate and di-n-butyl sebacate; and azelaate esters such as bis-2-ethylhexyl azelate; and chlorinated paraffin. Examples of suitable oils include paraffins such as paraffin, glycols such as polypropylene glycol, epoxy polymer plasticizers such as epoxidized soybean oil and epoxidized linseed oil, phosphate esters such as trioctyl phosphate and triphenyl phosphate, phosphites such as triphenyl phosphite, acrylic oligomers such as poly(n-butyl(meth)acrylate and poly(2-ethylhexyl(meth)acrylate), polybutene, polyisobutylene, polyisoprene, process oil, naphthenic oil, etc. These may be used alone or in combination of two or more.

[0082] Examples of the filler include inorganic fibers such as glass fibers and carbon fibers; organic fibers; and inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate.

[0083] Examples of curing agents include photocuring agents such as UV curing agents and heat curing agents, such as benzoins such as benzoin, α-methylolbenzoin, and α-t-butylbenzoin; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, α-methylolbenzoin methyl ether, α-methoxybenzoin methyl ether, and benzoin phenyl ether; benzophenone; anthraquinones such as 9,10-anthraquinone and 2-ethyl-9,10-anthraquinone; benzyl; acetophenones such as 2,2-dimethoxy-1,2-diphenylethan-1-one (2,2-dimethoxy-2-phenylacetophenone); and diacetyl. These curing agents may be used alone or in combination of two or more. By containing a curing agent, the pressure-sensitive adhesive can be suitably used as a curable pressure-sensitive adhesive such as a UV-curable hot-melt pressure-sensitive adhesive.

[0084] The pressure-sensitive adhesive layer (C) contains the acrylic pressure-sensitive adhesive in an amount of preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably substantially 100 parts by mass. The pressure-sensitive adhesive layer (C) may further contain other polymers in addition to the acrylic pressure-sensitive adhesive. Examples of the other polymers include olefin polymers such as polyethylene, ethylene-vinyl acetate copolymer (EVA resin), maleic anhydride-modified polyethylene, polypropylene, maleic anhydride-modified polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; styrene resins such as polystyrene, styrene-maleic anhydride copolymer, and high-impact polystyrene; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon 6, nylon 66, and polyamide elastomers; polycarbonate; polyvinyl chloride; polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl alcohol copolymer; polyacetal; polyvinylidene fluoride; polyurethane; modified polyphenylene ether; polyphenylene sulfide; silicone rubber-modified polymers; acrylic rubber; silicone rubber; and olefin rubbers such as isoprene rubber (IR), ethylene-propylene rubber (EPR), and ethylene-propylene-diene rubber (EPDM).

[0085] The method for producing the acrylic pressure-sensitive adhesive is not particularly limited, and for example, the acrylic pressure-sensitive adhesive can be produced by mixing the components using a known mixing or kneading device such as a kneader-ruder, an extruder, a mixing roll, or a Banbury mixer, usually at 100 to 250°C, and the obtained acrylic pressure-sensitive adhesive can be used to form the pressure-sensitive adhesive layer (C) by heating and melting it.

[0086] [Synthetic Rubber-Based Pressure-Sensitive Adhesive] The pressure-sensitive adhesive layer (C) preferably contains, as a synthetic rubber-based pressure-sensitive adhesive, an aromatic vinyl block copolymer (VI) containing a polymer block mainly composed of structural units derived from an aromatic vinyl monomer and a hydrogenated or non-hydrogenated polymer block mainly composed of structural units derived from a conjugated diene monomer. Here, "mainly composed" means that the polymer block contains 50% by mass or more of structural units derived from an aromatic vinyl monomer, based on the total mass of the polymer blocks, and that the hydrogenated or non-hydrogenated polymer blocks contain 50% by mass or more of structural units derived from a conjugated diene monomer. The content of the block copolymer (VI) in the pressure-sensitive adhesive layer (C) is preferably 10% by mass or more.

[0087] Examples of aromatic vinyl monomers constituting a polymer block mainly composed of structural units derived from an aromatic vinyl monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene (o,p-dimethylstyrene), vinylnaphthalene, and vinylanthracene, with styrene or α-methylstyrene being preferred among these. The polymer block mainly composed of structural units derived from an aromatic vinyl monomer may be formed from one or more of these aromatic vinyl monomers.

[0088] Examples of conjugated diene monomers constituting hydrogenated or non-hydrogenated polymer blocks mainly composed of structural units derived from conjugated diene monomers include 1,3-butadiene (butadiene), isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Among these, isoprene, butadiene, or a mixture thereof is preferred. The hydrogenated or non-hydrogenated polymer blocks mainly composed of structural units derived from conjugated diene monomers may be formed from one or more of these conjugated diene monomers.

[0089] In the hydrogenated or non-hydrogenated polymer block in the block copolymer (VI) mainly composed of structural units derived from a conjugated diene monomer, preferably 70% or more, more preferably 80% or more, and particularly preferably 95% or more of the carbon-carbon double bonds derived from the conjugated diene are hydrogenated.

[0090] By selecting a hydrogenated block copolymer having a hydrogenation rate of 70% or more, deterioration of the base polymer during extrusion molding can be suppressed, the heat resistance of the obtained adhesive article can be improved, and an adhesive article having the desired adhesive performance can be obtained.

[0091] The hydrogenation rate of the carbon-carbon double bond derived from the conjugated diene in the polymer block mainly composed of structural units derived from the conjugated diene monomer in the block copolymer (VI) can be determined, for example, by measuring the iodine value, using an infrared spectrophotometer, a nuclear magnetic resonance spectrometer, or the like.

[0092] In the block copolymer (VI), the content of the polymer block mainly composed of structural units derived from an aromatic vinyl monomer is preferably in the range of 3% by mass to 70% by mass, more preferably 10% by mass to 65% by mass. If the content of the polymer block is less than 3% by mass, the cohesive strength of the pressure-sensitive adhesive composition using the hydrogenated block copolymer as the base polymer is poor, and the extrusion moldability is reduced, making it difficult to form a good pressure-sensitive adhesive layer. On the other hand, if the content of the polymer block exceeds 70% by mass, the adhesive performance of the resulting pressure-sensitive adhesive layer is insufficient.

[0093] The number average molecular weight of the block copolymer (VI) is in the range of 50,000 to 200,000. If the number average molecular weight is less than 50,000, it is difficult to obtain a pressure-sensitive adhesive article with sufficient adhesive performance. On the other hand, if the number average molecular weight exceeds 200,000, even if the amount of polyethylene or tackifier resin added is adjusted, the melt viscosity of the pressure-sensitive adhesive composition becomes high, making extrusion molding difficult. The preferred number average molecular weight is in the range of 50,000 to 180,000.

[0094] In the block copolymer (VI), one or more polymer blocks mainly composed of structural units derived from an aromatic vinyl monomer are bonded to one or more hydrogenated or non-hydrogenated polymer blocks mainly composed of structural units derived from a conjugated diene monomer to form the block copolymer. The bonding mode of the polymer blocks is not limited, and may be linear, branched, or any combination thereof.

[0095] Furthermore, the hydrogenated or non-hydrogenated polymer block mainly composed of structural units derived from a conjugated diene monomer may have a functional group or a substituent such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, an epoxy group, or a halogen atom in the main chain or in a side chain including the terminal, within a range that does not impair the spirit of the present invention.

[0096] The method for obtaining the block copolymer (VI) is not particularly limited. For example, it can be obtained by sequentially polymerizing an aromatic vinyl monomer and a conjugated diene monomer in an inert organic solvent such as hexane or cyclohexane using an alkyllithium compound as an initiator, and then hydrogenating the resulting block copolymer by a known method. Aromatic vinyl block copolymers are also commercially available. The block copolymer (VI) may be used alone or in combination of two or more.

[0097] [Tackifying Resin] The synthetic rubber-based adhesive may contain a tackifying resin (VII). Examples of the tackifying resin include, from the viewpoint of facilitating adjustment of tack, adhesive strength, and holding power, rosins such as gum rosin, tall oil rosin, and wood rosin; modified rosins such as hydrogenated rosin, disproportionated rosin, and polymerized rosin; rosin-based resins such as rosin esters of these rosins and modified rosins, such as glycerin esters and pentaerythritol esters; terpene-based resins such as terpene resins mainly composed of α-pinene, β-pinene, dipentene, etc., aromatic modified terpene resins, hydrogenated terpene resins, and terpene phenolic resins; (hydrogenated) aliphatic (C5) petroleum resins; (hydrogenated) Examples of (hydrogenated) petroleum resins include aromatic (C9) petroleum resins, (hydrogenated) copolymer (C5 / C9) petroleum resins, (hydrogenated) dicyclopentadiene petroleum resins, and alicyclic saturated hydrocarbon resins; styrene polymers such as poly-α-methylstyrene, α-methylstyrene / styrene copolymers, styrene monomer / aliphatic monomer copolymers, styrene monomer / α-methylstyrene / aliphatic monomer copolymers, styrene monomer copolymers, and styrene monomer / aromatic monomer copolymers; and synthetic resins such as coumarone-indene resins, phenolic resins, and xylene resins. Among the above tackifying resins, rosin resins, terpene resins, (hydrogenated) petroleum resins, and styrene resins are preferred in terms of exhibiting high adhesive strength. These may be used alone or in combination of two or more.

[0098] As the styrene-based resin, commercially available products such as sx100 (manufactured by Yasuhara Chemical Co., Ltd.), FTR6000 series, and FTR8000 series (manufactured by Mitsui Chemicals, Inc.) can be used.

[0099] As the petroleum resin, commercially available products such as the Imave series (Idemitsu Kosan Co., Ltd.) and the Alcon series (Arakawa Chemical Industries Co., Ltd.) can be used.

[0100] [Softener] The synthetic rubber-based pressure-sensitive adhesive may contain a softener (VIII). Examples of softeners that can be used include known softeners such as paraffinic, naphthenic, and aromatic hydrocarbon oils; vegetable oils such as peanut oil and rosin; phosphate esters; low-molecular-weight polyethylene glycol; liquid paraffin; and hydrocarbon synthetic oils such as low-molecular-weight polyethylene, ethylene-α-olefin copolymer oligomer, liquid polybutene, liquid polyisoprene or its hydrogenated product, and liquid polybutadiene or its hydrogenated product. These may be used alone or in combination of two or more. Of these, paraffinic hydrocarbon oils and hydrocarbon synthetic oils such as ethylene-α-olefin copolymer oligomer are preferred. The kinematic viscosity of the softener (IV) at 40°C is preferably 50 to 1,000 mm from the viewpoints of moldability and ease of application. ２ / s, more preferably 50 to 800 mm ２ / s, more preferably 80 to 600 mm ２ / s.

[0101] The synthetic rubber-based pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer (C) preferably contains the block copolymer (VI), tackifier resin (VII) and softener (VIII) in proportions that satisfy the following formulas (i) and (j): 0.1≦W(VII) / W(VI)≦3.0 (i) 0.0≦W(VIII) / (W(VI)+W(VII))≦1.0 (j) (wherein W(VI), W(VII) and W(VIII) respectively represent the contents (by mass) of the block copolymer (VI), tackifier resin (VII) and softener (VIII) in the synthetic rubber-based pressure-sensitive adhesive).

[0102] As in the case of the acrylic pressure-sensitive adhesive described above, the synthetic rubber pressure-sensitive adhesive may further contain one or more additives such as a plasticizer, a heat stabilizer, a light stabilizer, an antistatic agent, a flame retardant, a foaming agent, a colorant, a dye, a refractive index adjuster, a filler, or a curing agent, as long as the effects of the present invention are not impaired.

[0103] The pressure-sensitive adhesive layer (C) preferably contains 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably substantially 100 parts by mass of the synthetic rubber-based pressure-sensitive adhesive. The pressure-sensitive adhesive layer (C) may further contain other polymers in addition to the synthetic rubber-based pressure-sensitive adhesive. Examples of the other polymers include olefin polymers such as polyethylene, ethylene-vinyl acetate copolymer (EVA resin), maleic anhydride-modified polyethylene, polypropylene, maleic anhydride-modified polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; styrene resins such as polystyrene, styrene-maleic anhydride copolymer, and high-impact polystyrene; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon 6, nylon 66, and polyamide elastomers; polycarbonate; polyvinyl chloride; polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl alcohol copolymer; polyacetal; polyvinylidene fluoride; polyurethane; modified polyphenylene ether; polyphenylene sulfide; silicone rubber-modified polymers; acrylic rubber; silicone rubber; and olefin rubbers such as isoprene rubber (IR), ethylene-propylene rubber (EPR), and ethylene-propylene-diene rubber (EPDM).

[0104] The method for producing the synthetic rubber-based pressure-sensitive adhesive is not particularly limited, and for example, the synthetic rubber-based pressure-sensitive adhesive can be produced by mixing the components using a known mixing or kneading device such as a kneader-ruder, an extruder, a mixing roll, or a Banbury mixer, usually at 100 to 250°C, and the obtained synthetic rubber-based pressure-sensitive adhesive can be used to form the pressure-sensitive adhesive layer (C) by heating and melting it.

[0105] (Thickness ratio of thermoplastic polymer composition layer (A), cured resin layer (B), and pressure-sensitive adhesive layer (C)) In one preferred embodiment of the laminate of the present invention, the thicknesses of the thermoplastic polymer composition layer (A), cured resin layer (B), and pressure-sensitive adhesive layer (C) satisfy the following formulas (g) and (h): 0.02≦T(B) / T(A)≦0.30 (g) 0.04≦T(C) / (T(A)+T(B))≦0.50 (h) (wherein T(A), T(B), and T(C) respectively represent the thicknesses (mm) of the thermoplastic polymer composition layer (A), cured resin layer (B), and pressure-sensitive adhesive layer (C) constituting the laminate).

[0106] In formula (g), when the value of "T(B) / T(A)" (i.e., the ratio of the thickness of the cured resin layer (B) to the thickness of the thermoplastic polymer composition layer (A)) is 0.02 or more, resistance to scratches and impacts is easily maintained. Furthermore, when the value is 0.30 or less, the layer made of the cured resin does not become too thick, making it less likely to break when bent or stretched. The value of "T(B) / T(A)" is preferably 0.02 to 0.30, more preferably 0.03 to 0.28, even more preferably 0.04 to 0.24, and particularly preferably 0.05 to 0.20. Furthermore, in formula (h), when the value of "T(C) / (T(A)+T(B))" (i.e., the ratio of the thickness of the pressure-sensitive adhesive layer (C) to the total thickness of the thermoplastic polymer composition layer (A) and the cured resin layer (B)) is 0.04 or more, the laminate is more likely to exhibit sufficient adhesive strength. Furthermore, if the T(C) / (T(A)+T(B)) value is 0.50 or less, adhesive residue is less likely to be left behind when the laminate is peeled off from the adherend. The value of "T(C) / (T(A)+T(B))" is preferably 0.04 to 0.50, more preferably 0.06 to 0.45, and even more preferably 0.08 to 0.40.

[0107] In the laminate of the present invention, the thickness of the thermoplastic polymer composition layer (A) is preferably 100 to 300 μm, more preferably 110 to 250 μm, and even more preferably 120 to 220 μm. When the thickness of the thermoplastic polymer composition layer (A) is 300 μm or less, the laminate does not become too hard and is easy to handle. Furthermore, when the thickness is 100 μm or more, the strength of the laminate can be maintained and sufficient protective performance is likely to be exhibited when used as a protective film. The form of the laminate of the present invention in the stage prior to application to various uses is not particularly limited, but examples include a form in which sheets are stacked together or a form wound into a roll.

[0108] The thickness variation (difference between the maximum and minimum thicknesses) of the thermoplastic polymer composition layer (A) is preferably 25 μm or less, more preferably 20 μm or less, even more preferably 17 μm or less, and even more preferably 15 μm or less. Furthermore, the thickness variation coefficient, which is expressed as the ratio of thickness variation to the average thickness (actually measured value) of the thermoplastic polymer composition layer (A), is preferably 5% or less, preferably 4% or less, more preferably 3% or less, and even more preferably 2% or less. The thickness variation coefficient can be calculated using the following formula: (thickness variation coefficient) [%] = (thickness variation) / (average thickness) × 100.

[0109] There is no particular limitation on the number of layers constituting the laminate of the present invention, and as long as they are laminated in the order of (B), (A), and (C), another layer may be laminated between each of the layers. For example, another layer such as a release layer may be laminated on the surface of the pressure-sensitive adhesive layer (C) opposite to the surface that contacts the thermoplastic polymer composition layer (A), or another layer such as a printed layer may be laminated on the surface that contacts the thermoplastic polymer composition layer (A).

[0110] (Properties of the Laminate) In the laminate of the present invention, the 180° peel strength at a peel rate of 300 mm / min after 24 hours from lamination to an automotive steel plate (product name: SPCC-SD, manufactured by Nippon Test Panel Co., Ltd.), measured at room temperature (23°C) in accordance with JIS Z 0237:2022, is preferably 10 to 25 N / 25 mm, more preferably 15 to 25 N / 25 mm, and even more preferably 18 to 25 N / 25 mm. For example, when the laminate of the present invention is used as a protective film, if the peel strength to the automotive steel plate (adherend) is low, the laminate may not adhere to the adherend with sufficient strength during lamination to the automotive steel plate, and may easily peel off. If the peel strength is too high, the peeling operation becomes difficult, and attempting to forcibly peel the laminate may result in deformation of the adherend itself.

[0111] (Method for producing laminate) The method for producing the laminate of the present invention is not particularly limited, and any method can be used, such as coextrusion molding or solution coating on the thermoplastic polymer composition layer (A). From the viewpoint of cost, the method for producing the laminate is preferably a coextrusion molding method using a feed block or a multi-manifold die, and further using a film-forming device such as a T-die extruder or an inflation molding machine. Furthermore, from the viewpoint of transparency when formed into a laminate, solution coating on the thermoplastic polymer composition layer (A) can also be preferably used. A production method including laminating the thermoplastic polymer composition layer (A) and the pressure-sensitive adhesive layer (C) by melt coextrusion is also a preferred embodiment.

[0112] [Uses] The laminate of the present invention can be used for various uses, such as pressure-sensitive adhesive tapes and films for surface protection, masking, bundling, packaging, office use, labeling, decoration / display, bonding, dicing tape, sealing, corrosion prevention / waterproofing, medical / hygienic use, shatterproofing of glass, electrical insulation, holding and fixing electronic devices, semiconductor manufacturing, optical display films, pressure-sensitive adhesive optical films, electromagnetic wave shielding, or sealing materials for electric / electronic components.

[0113] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The components used in the examples and comparative examples and their properties are shown in Tables 1 to 8 below.

[0114] The weight-average molecular weight was determined by gel permeation chromatography (GPC) under the following conditions, and expressed as a value converted into standard polystyrene: Column: "TSKgel G4000HXL" (trade name) x 2, manufactured by Tosoh Corporation (column temperature: 40°C) Mobile phase: tetrahydrofuran (flow rate: 1 ml / min) Detector: differential refractometer (further connected to a multi-wavelength detector (detection wavelength: 254 nm)) Standard substance: TSK standard polystyrene, manufactured by Tosoh Corporation Sample concentration: 0.06 mass%

[0115] The average degree of polymerization was measured at 20° C. using an automatic dilution type capillary viscometer (Ubbelohde type, capillary inner diameter=0.5 mm) using chloroform as a solvent, and calculated as a PMMA-equivalent degree of polymerization.

[0116] [Block Copolymer (I)] Block Copolymer (1) "Septon (registered trademark) Q-1250" (polymer block P: poly(α-methylstyrene), polymer block Q: polybutadiene (hydrogenation rate of 90% or more), weight average molecular weight of 78,700), manufactured by Kuraray Co., Ltd.) Block Copolymer (2) "Septon (registered trademark) 4033" (polymer block P: polystyrene, polymer block Q: polybutadiene (hydrogenation rate of 90% or more), weight average molecular weight of 97,500), manufactured by Kuraray Co., Ltd.

[0117]

[0118] [Acrylic Resin (II)] Acrylic Resin (3) "PARAPET (registered trademark) G" (Methyl methacrylate unit content = 85% by mass, content of vinyl monomer units copolymerizable with methyl methacrylate units = 15% by mass or less, average degree of polymerization = 1,000, MFR = 8 g / 10 min (measured in accordance with JIS K 7210-1:2014, conditions: 230°C, 37.3N), manufactured by Kuraray Co., Ltd.) Acrylic Resin (4) "PARAPET (registered trademark) GF" (Methyl methacrylate unit content = 85% by mass, content of vinyl monomer units copolymerizable with methyl methacrylate units = 15% by mass or less, average degree of polymerization = 1,000, MFR = 15 g / 10 min (measured in accordance with JIS K 7210-1:2014, conditions: 230°C, 37.3N), manufactured by Kuraray Co., Ltd.) Acrylic resin (5) "PARAPET (registered trademark) GH-S" (content of methyl methacrylate units = 90% by mass, content of vinyl monomer units copolymerizable with methyl methacrylate units = 10% by mass or less, average degree of polymerization = 1,200, MFR = 10 g / 10 min (measured in accordance with JIS K 7210-1:2014, conditions: 230°C, 37.3N), manufactured by Kuraray Co., Ltd.) Acrylic resin (6) "PARAPET (registered trademark) LW" (content of methyl methacrylate units = 85% by mass, content of vinyl monomer units copolymerizable with methyl methacrylate units = 15% by mass or less, average degree of polymerization = 500, MFR = not measurable due to high fluidity (measured in accordance with JIS K 7210-1:2014, conditions: 230°C, 37.3N), manufactured by Kuraray Co., Ltd.) Acrylic resin (7) "PARAPET (registered trademark) HR-G" (methyl methacrylate unit content = 95% by mass, content of vinyl monomer units copolymerizable with methyl methacrylate units = 5% by mass or less, average degree of polymerization = 1,800, MFR = 0.5 g / 10 min (measured in accordance with JIS K 7210-1:2014, conditions: 230°C, 37.3N), manufactured by Kuraray Co., Ltd.) Acrylic resin (8) "METABLEN (registered trademark) P-570A" (methyl methacrylate unit content = 95% by mass, content of vinyl monomer units copolymerizable with methyl methacrylate units = 5% by mass or less, average degree of polymerization = 2,700, MFR = < 0.1 g / 10 min (measured in accordance with JIS K 7210-1:2014).Conditions: 230°C, 37.3N), manufactured by Mitsubishi Chemical Corporation.

[0119]

[0120] [Acrylic Resin (III)] Acrylic Resin (9) "Metablen (registered trademark) P-551A" (content of methyl methacrylate units = 84% by mass, content of vinyl monomer units copolymerizable with methyl methacrylate units = 16% by mass or less, average degree of polymerization = 14,500, MFR = < 0.1 g / 10 min (measured in accordance with JIS K 7210-1:2014, conditions: 230 °C, 37.3 N), manufactured by Mitsubishi Chemical Corporation) Acrylic Resin (10) "Metablen (registered trademark) P-550A" (content of methyl methacrylate units = 88% by mass, content of vinyl monomer units copolymerizable with methyl methacrylate units = 12% by mass or less, average degree of polymerization = 9,500, MFR = < 0.1 g / 10 min (measured in accordance with JIS K 7210-1:2014, conditions: 230 °C, 37.3 N), manufactured by Mitsubishi Chemical Corporation) 7210-1:2014, conditions: 230°C, 37.3N), manufactured by Mitsubishi Chemical Corporation) Acrylic resin (11) "Metablen (registered trademark) P-530A" (content of methyl methacrylate units = 80% by mass, content of vinyl monomer units copolymerizable with methyl methacrylate units = 20% by mass or less, average degree of polymerization = 31,000, MFR = < 0.1 g / 10 min (measured in accordance with JIS K 7210-1:2014, conditions: 230°C, 37.3N), manufactured by Mitsubishi Chemical Corporation) Acrylic resin (12) "Metablen (registered trademark) P-531A" (content of methyl methacrylate units = 80% by mass, content of vinyl monomer units copolymerizable with methyl methacrylate units = 20% by mass or less, Average degree of polymerization = 47,000, MFR = < 0.1 g / 10 min (measured in accordance with JIS K 7210-1:2014, conditions: 230 ° C, 37.3 N), manufactured by Mitsubishi Chemical Corporation)

[0121]

[0122] [Softener (IV)] Softener (13) "Diana Process Oil PW380" (kinematic viscosity (40°C) = 386.1 mm ２ / s, paraffin-based process oil, manufactured by Idemitsu Kosan Co., Ltd.)

[0123]

[0124] [Laminate] [Layer (B) made of cured resin] (14) Two-component reactive cured resin containing urethane (meth)acrylate resin as the main material and containing fluorine and silicon atoms

[0125]

[0126] [Layer (C) made of adhesive] (15) Acrylic adhesive mainly composed of "CLARITY (registered trademark) LA3320" (acrylic block copolymer with polymer block R content = 18 mass %)

[0127]

[0128] (16) LOCTITE DURO-TAK2835 (a commercially available acrylic adhesive containing a crosslinking agent, manufactured by Henkel)

[0129]

[0130] (17) Synthetic rubber adhesive mainly composed of "Septon (registered trademark) 2063" and containing FTR8100 (styrene-based resin, manufactured by Mitsubishi Chemical Corporation) as a tackifier resin.

[0131]

[0132] Examples 1 to 15 and Comparative Examples 1 to 7 The components were premixed in a supermixer at the mass ratios shown in Table 1, then melt-kneaded using a twin-screw extruder and cut using an underwater cut method to obtain pellets of a thermoplastic polymer composition. The resulting pellets of the thermoplastic polymer composition were extruded using a single-screw extruder at a cylinder temperature of 240°C, a die head temperature of 245°C, and a cast roll temperature of 25°C, connected to a film molding machine, and a 150 μm thick, 30 cm wide film was produced using the T-die method. Using the thermoplastic polymer composition and the 150 μm thick film produced therefrom, physical properties were measured and evaluated as follows. The evaluation results are shown in Tables 9-1 to 9-5 and Tables 10-1 to 10-2.

[0133] [Transparency] Transparency was evaluated using the haze value of a 150 μm thick film measured using a turbidity / haze meter "HR-100" (manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K 7136:2000. The lower the haze value, the better the transparency, with less than 2.0 being rated as ◯, 2.0 to 3.0 being △, and more than 3.0 being x.

[0134] [Film Thickness Variation] A 150 μm thick film was sampled in a length of 100 cm and divided into grids of 5 cm in the MD and 5 cm in the TD. The thickness at the center of each of 120 grids was measured in accordance with JIS K 7130:1999. The difference between the maximum and minimum measured thicknesses was taken as the film thickness variation. Film thickness variation of 15 μm or less was rated as ◯, more than 15 to 25 μm was rated as △, and more than 25 μm was rated as ×. The film thickness variation coefficient was also calculated using the following formula, and a film thickness variation coefficient of 5% or less was rated as ◯, and more than 5% was rated as ×. (Film thickness variation coefficient) [%] = (film thickness variation) / (average film thickness) × 100

[0135] [Melt Tension] Using a melt tension measuring device of a capillary rheometer, a pellet-shaped thermoplastic polymer composition was extruded at an extrusion temperature of 230°C through a capillary having a diameter of 1 mm and a length of 10 mm at a piston speed of 5 mm / min, and a strand was taken up, and the tension at which the strand broke was measured to evaluate the melt tension. Tensions of 30 kPa or more were rated as ◯, tensions of 20 kPa or more but less than 30 kPa as △, and tensions less than 20 kPa as x.

[0136] [Extensibility] A pellet-shaped thermoplastic polymer composition was extruded at an extrusion temperature of 230°C through a capillary having a diameter of 1 mm and a length of 10 mm at a piston speed of 5 mm / min using a melt tension measuring device of a capillary rheometer, and the strand was taken up to measure the breaking speed of the strand to evaluate extensibility. A breaking speed of 40 m / min or more was rated as ◯, a breaking speed of 35 m / min or more but less than 40 m / min as △, and a breaking speed less than 35 m / min as x.

[0137] [Tear Strength (MD, TD)] A 150 μm thick film was punched into an unnotched angle-shaped test piece according to JIS K 6252-1:2015, and the tear strength in the MD direction at room temperature was measured. The tear strength in the TD direction was also measured. Tear strengths of 400 N / cm or more were rated as ◯, those of 300 N / cm or more but less than 400 N / cm as △, and those of less than 300 N / cm as ×.

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145] Tables 9-1 to 9-5 show that the 150 μm thick films molded using the thermoplastic polymer compositions of Examples 1 to 15 exhibited good transparency, high moldability (film thickness stability), and low anisotropy. On the other hand, as shown in Table 10-1, Comparative Example 1, in which block copolymer (2) in which polymer block P was composed of polystyrene was used as block copolymer (I), resulted in significantly poor film transparency and moldability. Comparative Example 2, in which acrylic resin (6) with a high average polymerization degree was used as acrylic resin (II), resulted in increased film haze and reduced transparency. Comparative Example 3, in which acrylic resin (9) with a high average polymerization degree was used as acrylic resin (III), resulted in decreased melt tension and poor moldability. Comparative Example 4, in which acrylic resin (III) was not blended, exhibited significant film thickness fluctuations, making stable film molding impossible. Furthermore, as shown in Table 10-2, Comparative Example 5, in which an excessive amount of block copolymer (I) was used, exhibited significant film thickness fluctuations, making stable film molding impossible. In Comparative Example 6, in which an excessive amount of acrylic resin (II) was used, the haze of the film increased and the transparency decreased. In Comparative Example 7, in which an excessive amount of acrylic resin (III) was used, the haze of the film increased, the transparency decreased, and the extensibility decreased.

[0146] Examples 16 to 20 and Comparative Example 8 In Examples 16 to 20 and Comparative Example 8, a three-layer laminate was prepared in which a 150 μm or 250 μm thick film made of the thermoplastic polymer composition of Example 2 was used as the thermoplastic polymer composition layer (A), and a cured resin layer (B) and a pressure-sensitive adhesive layer (C) were provided in the order (B)-(A)-(C). In Examples 16 to 19, the laminates were prepared by solution coating both the cured resin layer (B) and the pressure-sensitive adhesive layer (C). In Example 20, the thermoplastic polymer composition layer (A) and the pressure-sensitive adhesive layer (C) were laminated by coextrusion molding (melt coextrusion), and the cured resin layer (B) was laminated by solution coating onto the thermoplastic resin layer (A) of the resulting laminate. In Comparative Example 8, the cured resin layer (B) was laminated onto the thermoplastic polymer composition layer (A) by solution coating, but the pressure-sensitive adhesive layer (C) was not laminated. The physical properties of the prepared laminates were measured and evaluated as follows. The evaluation results are shown in Table 11.

[0147] [Adhesion] The 180° peel strength of the laminate was measured at room temperature at a peel rate of 300 mm / min 24 hours after lamination to an automotive steel plate (product name: SPCC-SD, manufactured by Nippon Test Panel Co., Ltd.) in accordance with JIS Z 0237: 2022 to evaluate adhesion. Adhesion strength of 10 to 25 N / 25 mm was evaluated as ◯, and adhesion strength of less than 10 N / 25 mm or more than 25 N / 25 mm was evaluated as ×.

[0148] [Adhesive Residue] The laminate was subjected to a 180° peel test at room temperature at a peel rate of 300 mm / min against an automotive steel plate (product name: SPCC-SD, manufactured by Nippon Test Panel Co., Ltd.) 24 hours after lamination in accordance with JIS Z 0237:2022, and adhesive residue on the automotive steel plate at that time was evaluated visually. Those that did not leave adhesive residue were marked with ◯, and those that did leave adhesive residue were marked with ×.

[0149]

[0150] It can be seen from Table 11 that the laminates of Examples 16 to 20 exhibited high adhesion to automotive steel plates while leaving no adhesive residue. On the other hand, in Comparative Example 8, in which the pressure-sensitive adhesive layer (C) was not laminated, the tackiness of the thermoplastic polymer composition layer (A) was insufficient to provide adhesion to coated automotive steel plates, and the laminate could not be suitably used as a protective film.

Claims

1. A block copolymer (I) containing a polymer block P mainly composed of α-methylstyrene units and a hydrogenated or non-hydrogenated polymer block Q mainly composed of conjugated diene or isobutylene units, and having a weight average molecular weight of 30,000 to 200,000; an acrylic resin (II) containing 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith, and having an average degree of polymerization of 400 to 2,000; an acrylic resin (III) containing 50% by mass or more of methyl methacrylate units and 50% by mass or less of vinyl monomer units copolymerizable therewith, and having an average degree of polymerization of 6,000 to 40,000; and optionally a softener (IV), which are mixed in a manner such that W(II) / W(I) satisfies the following formulas (a), (b), and (c): 0.1≦W(II) / W(I)≦2.4 (a) 0.001≦W(III) / (W(I)+W(II))≦0.04 (b) 0≦W(IV) / (W(I)+W(II)+W(III)+W(IV))≦0.5 (c) wherein W(I), W(II), W(III) and W(IV) represent the contents (by mass) of the block copolymer (I), acrylic resin (II), acrylic resin (III) and softener (IV) in the thermoplastic polymer composition, respectively.

2. The thermoplastic polymer composition according to claim 1, wherein the acrylic resin (II) has a melt flow rate of 5 to 25 g / 10 min at 230° C. and 37.3 N.

3. The thermoplastic polymer composition according to claim 1, wherein the tension at which the strand breaks is 30 kPa or more when a strand is extruded at a piston speed of 5 mm / min from a capillary having a diameter of 1 mm and a length of 10 mm at an extrusion temperature of 230°C using a melt tension measuring device of a capillary rheometer and taken up.

4. The thermoplastic polymer composition according to claim 1, wherein when a strand is extruded at an extrusion temperature of 230°C through a capillary having a diameter of 1 mm and a length of 10 mm at a piston speed of 5 mm / min using a melt tension measuring device of a capillary rheometer and then taken up, the speed at which the strand breaks is 40 m / min or more.

5. The thermoplastic polymer composition according to claim 1, wherein the film thickness variation coefficient measured in accordance with JIS K 7130:1999 using a film formed to a thickness of 150 μm using an extruder is 5% or less, and the tear strength in both the machine direction and the transverse direction measured at room temperature using an unnotched angle-shaped test piece in accordance with JIS K 6252-1:2015 is 400 N / cm or more.

6. A sheet or film comprising the thermoplastic polymer composition according to any one of claims 1 to 5.

7. A laminate having a layer (A) made of the thermoplastic polymer composition according to claim 1, a layer (B) made of a cured resin, and a layer (C) made of an adhesive, which are laminated in the order of (B)-(A)-(C).

8. The laminate according to claim 7, wherein the thicknesses of the layer (A) made of the thermoplastic polymer composition, the layer (B) made of the cured resin, and the layer (C) made of the adhesive are in proportions that satisfy the following formulas (g) and (h): 0.02≦T(B) / T(A)≦0.30 (g) 0.04≦T(C) / (T(A)+T(B))≦0.50 (h) [wherein T(A), T(B), and T(C) represent the thicknesses (mm) of the layer (A) made of the thermoplastic polymer composition, the layer (B) made of the cured resin, and the layer (C) made of the adhesive, respectively].

9. The laminate according to claim 7, wherein the layer (A) made of the thermoplastic polymer composition has a thickness of 100 to 300 μm.

10. The laminate according to claim 7, wherein the pressure-sensitive adhesive layer (C) contains an aromatic vinyl block copolymer (VI) containing a polymer block mainly composed of structural units derived from an aromatic vinyl monomer and a hydrogenated or non-hydrogenated polymer block mainly composed of structural units derived from a conjugated diene monomer.

11. The laminate according to claim 10, wherein the layer (C) made of the pressure-sensitive adhesive contains an aromatic vinyl block copolymer (VI), a tackifying resin (VII), and optionally a softener (VIII) in proportions that satisfy the following formulas (i) and (j): 0.1≦W(VII) / W(VI)≦3.0 (i) 0.0≦W(VIII) / (W(VI)+W(VII))≦1.0 (j) [wherein W(VI), W(VII), and W(VIII) respectively represent the contents (by mass) of the block copolymer (VI), tackifying resin (VII), and softener (VIII) in the layer (C) made of the pressure-sensitive adhesive composite].

12. The laminate according to claim 7, wherein the layer (B) made of the cured resin contains a urethane (meth)acrylate resin.

13. The laminate according to claim 12, wherein the urethane (meth)acrylate resin contains fluorine atoms and silicon atoms.

14. A method for producing a laminate according to claim 7, comprising laminating the layer (A) made of the thermoplastic polymer composition and the layer (C) made of the pressure-sensitive adhesive by melt co-extrusion.

15. A protection film or protection sheet comprising the laminate according to any one of claims 8 to 13.

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