Modified polyethylene terephthalate molded body, its manufacturing method, and copolymer solution

Abstract

Provided is a method for manufacturing a modified polyethylene terephthalate molded product having excellent surface characteristics. A method for manufacturing a modified polyethylene terephthalate molded product having a contact step for bringing a polyethylene terephthalate molded product and a copolymer solution containing a side chain crystalline block copolymer and a solvent into contact with each other. The side chain crystalline block copolymer includes a first polymerization block, which is a repetition of constituent units having an alkyl group having 8 or more carbon atoms in a side chain, and a second polymerization block, which is a repetition of constituent units having a functional group. The solvent has (i) an ester-based solvent having a boiling point at 1 atm of 150°C or above or (ii) an aprotic polar solvent having permittivity of 30 or above.

Description

[Technical Field]

[0001] The present invention relates to a modified polyethylene terephthalate molded article and a method for producing the same. The present invention also relates to a copolymer solution. [Background technology]

[0002] Polyethylene terephthalate (PET) is a plastic that is widely used in fibers, bolts, sheets, etc. due to its excellent insulating properties, chemical resistance, and abrasion resistance. However, it is a plastic that lacks adhesiveness, hydrophilicity, and dyeability.

[0003] Currently, methods such as plasma treatment and corona treatment are mainly used as modification methods for improving the adhesiveness, hydrophilicity, dyeability, etc. of PET (e.g., Non-Patent Document 1, Non-Patent Document 2, etc.). Due to their nature, plasma treatment and corona treatment cannot be applied to complex shapes such as cylindrical shapes, and there are also issues such as the extremely high cost of introducing the equipment.

[0004] Meanwhile, the present inventors have disclosed a method for modifying the surface of fluororesin, polyethylene resin, or polypropylene resin by using a side chain crystalline block copolymer (SCCBC).

[0005] For example, Patent Document 1 discloses a method for modifying a fluororesin using a copolymer having structural units derived from a first monomer (A) and structural units derived from a second monomer (B), wherein the monomer (A) is any monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, having any fluorinated alkyl group selected from the group consisting of formulae (a1) to (a5) in its side chain, and the monomer (B) is a monomer having a functional group.

[0006] Patent Document 2 discloses a surface modification material comprising a substrate at least a portion of which is polyethylene, and a polymer that modifies the surface of the polyethylene, wherein the polymer is a block copolymer of monomers including a first monomer that is an acrylate having an alkane chain with 10 or more carbon atoms and a second monomer that is an acrylate of a tertiary amine, or a block copolymer of monomers including a first monomer that is a (meth)acrylate having an alkane chain with 10 or more carbon atoms and a second monomer that is a (meth)acrylate having a side chain with 4 or more carbon atoms and a -CF2- structure.

[0007] Patent Document 3 discloses a method for modifying a polypropylene resin molded body, which includes a step of contacting a copolymer solution containing a side-chain crystalline block copolymer with a polypropylene resin molded body at a temperature of 40 to 120°C. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-079389 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-229725 [Patent Document 3] Japanese Patent Application Publication No. 2019-137779 [Non-patent literature]

[0009] [Non-Patent Document 1] Ming Gao et al., Modification of polyethylene terephthalate (PET) films surface with gradient roughness and homogenous surface chemistry by dielectric barrier discharge plasma, Chemical Physics Letter, vol 689, pp. 179-184, 2017 [Non-patent document 2] Weilin Xu et al., Surface modification of polyester fabric by corona discharge irradiation, European Polymer Journal, vol 39, pp. 199-202, 2003 Summary of the Invention [Problem to be solved by the invention]

[0010] As mentioned above, PET needs to be modified to improve its adhesiveness, hydrophilicity, dyeability, etc. However, conventional methods have limitations on the shapes that can be modified and require special equipment. Therefore, a simple method for modifying the PET surface has been sought to obtain modified polyethylene terephthalate molded articles with good adhesive properties, etc.

[0011] In addition, in the methods disclosed in Patent Documents 1 to 3, the resin to be modified is a vinyl resin, and the target resin is modified using SCCBC, which has a structure in its side chain that is relatively similar to that of the resin to be modified. However, the SCCBCs disclosed in Patent Documents 1 to 3 do not have significant similarities to condensation resins such as PET resins, which are the target of modification in the present invention. To date, modification of resins that do not have significant similarities to SCCBC using SCCBC has not been fully investigated.

[0012] An object of the present invention is to provide a modified polyethylene terephthalate molded article having excellent surface properties and a method for producing the same. [Means for solving the problem]

[0013] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the following invention meets the above object, thereby completing the present invention.

[0014] That is, the present invention relates to the following inventions. <1> a contacting step of contacting a polyethylene terephthalate molded article with a copolymer solution containing a side-chain crystalline block copolymer and a solvent, the side-chain crystalline block copolymer comprises a first polymer block which is a repeat of a structural unit having an alkyl group having 8 or more carbon atoms in a side chain, and a second polymer block which is a repeat of a structural unit having a functional group; A method for producing a modified polyethylene terephthalate molded article, wherein the solvent contains the following (i) or (ii): (i) Ester solvents with a boiling point of 150°C or higher at 1 atm (ii) aprotic polar solvents with a dielectric constant of 30 or more <2> the ester solvent comprises a phthalate ester compound, In the contacting step, the copolymer solution is brought into contact with the polyethylene terephthalate molded article at 80° C. or higher. <1> A method for producing the modified polyethylene terephthalate molded article described in claim 1. <3> the phthalate ester compound is any one selected from the group consisting of dimethyl phthalate, diethyl phthalate, and dioctyl phthalate; <2> The manufacturing method described in <4> The contact is carried out at a temperature of 120°C or higher and 200°C or lower. <2> or <3> The manufacturing method described in <5> the aprotic polar solvent having a dielectric constant of 30 or more includes dimethyl sulfoxide and / or N-methyl-2-pyrrolidone; In the contacting step, the copolymer solution is brought into contact with the polyethylene terephthalate molded article at a temperature of 20°C or higher and 120°C or lower. <1> A method for producing the modified polyethylene terephthalate molded article described in claim 1. <6> the first polymer block is a polymer of any one monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, each having an alkyl group having 8 or more carbon atoms; <1> from <5> 1. The manufacturing method according to any one of the preceding claims. <7> the second polymer block is a repeat of a structural unit having a polar group in a side chain, <1> from <6> 1. The manufacturing method according to any one of the preceding claims. <8> A polyethylene terephthalate molded body and a functional layer containing a side-chain crystalline block copolymer formed on at least a part of the surface of the molded body, the side-chain crystalline block copolymer comprises a first polymer block which is a repeat of a structural unit having an alkyl group having 8 or more carbon atoms in a side chain, and a second polymer block which is a repeat of a structural unit having a functional group; A modified polyethylene terephthalate molded body, wherein the peel strength of the functional layer in a T-peel test is 0.5 N / mm or more. <9> the second polymer block is a repeat of a structural unit having a polar group in a side chain, <8> The modified polyethylene terephthalate molded article according to claim 1. <10> the second polymer block is a repeat of a structural unit having an amino group, a carboxyl group, or an oxyalkylene group on a side chain; <8> or <9> The modified polyethylene terephthalate molded article according to any one of the preceding claims. <11> the weight average molecular weight of the first polymer block is 5,000 or more; The weight average molecular weight of the second polymer block is 5,000 or more. <8> from <10> The modified polyethylene terephthalate molded article according to any one of the preceding claims. <12> a portion containing the side chain crystalline block copolymer remains on the surface even after contact with a good solvent for the side chain crystalline block copolymer; <8> from <11> The modified polyethylene terephthalate molded article according to any one of the preceding claims. <13> A copolymer solution containing a side-chain crystalline block copolymer and a solvent, the side chain crystalline block copolymer comprises a block (A) derived from a (meth)acrylate having an alkyl group having 8 or more carbon atoms and a block (B) having a polar group in the side chain, the concentration of the side chain crystalline block copolymer is 0.01 to 2.0% by mass, A copolymer solution, wherein the solvent comprises the following (i) or (ii): (i) Ester solvents with a boiling point of 150°C or higher at 1 atm (ii) aprotic polar solvents with a dielectric constant of 30 or more [Effects of the Invention]

[0015] According to the present invention, there are provided a modified polyethylene terephthalate molded article having excellent surface properties and a method for producing the same. For example, according to the present invention, there are provided a modified polyethylene terephthalate molded article having good adhesion and a method for producing the same. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 is a diagram for explaining a test piece used in a peel test in an example of the present invention and a method for calculating data. [Figure 2] FIG. 1 is a diagram showing the results of FT-IR analysis of a modified PET film according to an example of the present invention. [Figure 3] FIG. 1 shows the results of evaluating the adhesiveness of modified PET films modified at different modification temperatures using a copolymer solution (STA-TBAEMA, DEP). [Figure 4] FIG. 1 shows the results of evaluating the adhesiveness of modified PET films modified with diethyl phthalate alone or with a copolymer solution (STA-TBAEMA, DEP). [Figure 5]FIG. 1 shows the results of evaluating the adhesiveness of modified PET films that were modified using a copolymer solution (STA-TBAEMA, DEP) for different immersion times. [Figure 6] FIG. 1 shows the results of evaluating the adhesiveness of modified PET films that were modified using a copolymer solution (STA-TBAEMA, DEP) for different immersion times. [Figure 7] FIG. 1 shows the results of evaluating the adhesiveness of modified PET films modified with copolymer solutions (STA-TBAEMA, DEP) having different SCCBC concentrations. [Figure 8] FIG. 1 shows the results of evaluating the adhesiveness of a copolymer solution (STA-TBAEMA, DEP) and modified PET films modified under different butyl acetate washing conditions. [Figure 9] FIG. 1 shows the results of evaluating the adhesiveness of modified PET films modified at different modification temperatures using a copolymer solution (STA-TBAEMA, NMP). [Figure 10] FIG. 1 shows the results of evaluating the adhesiveness of modified PET films modified at different modification temperatures using a copolymer solution (STA-TBAEMA, DMSO). DETAILED DESCRIPTION OF THE INVENTION

[0017] The following describes in detail an embodiment of the present invention, but the following description of the constituent elements is one example (typical example) of an embodiment of the present invention, and the present invention is not limited to the following content unless the gist of the present invention is changed. Note that when the expression "to" is used in this specification, it is used as an expression including the numerical values or physical property values before and after it.

[0018] <Method for producing modified polyethylene terephthalate molded article> The present invention relates to a method for producing a modified polyethylene terephthalate molded article (hereinafter sometimes referred to as the "method for producing the modified PET of the present invention"), which includes a contacting step of contacting a copolymer solution containing a side-chain crystalline block copolymer and a solvent with a polyethylene terephthalate molded article, wherein the side-chain crystalline block copolymer comprises a first polymer block that is a repeating structural unit having an alkyl group having 8 or more carbon atoms in the side chain, and a second polymer block that is a repeating structural unit having a functional group.

[0019] The present inventors have found that PET molded articles can be modified by contacting them with a copolymer solution containing the side-chain crystalline block copolymer (hereinafter simply referred to as "block copolymer") and a solvent. Contact with the copolymer solution loosens and swells the PET surface, allowing the alkyl groups with 8 or more carbon atoms in the side chains of the first polymer block to penetrate into the PET, resulting in adhesion between the PET molded article and the block copolymer, imparting the functionality of the block copolymer to the PET molded article.

[0020] [First Polymer Block] The first polymer block (hereinafter referred to as "block (A)") is a repeating structural unit having an alkyl group with 8 or more carbon atoms in the side chain. In block (A), the alkyl group with 8 or more carbon atoms in the side chain is bonded directly to the main chain of block (A) or via a linking group (ester bond, amide bond, ether bond, benzene ring, etc.). This block (A) becomes the part that exhibits side chain crystallinity due to the alkyl group in the side chain. It is presumed that this side chain crystalline part interacts with the PET molded article. The adhesion between the block copolymer and the PET molded article can be adjusted depending on the number of carbon atoms and structure of the side chain of block (A).

[0021] The alkyl group having 8 or more carbon atoms in the side chain of block (A) preferably has 10 or more carbon atoms, more preferably 12 or more carbon atoms, and even more preferably 14 or more carbon atoms. The alkyl group is preferably a linear alkyl group. The upper limit can be appropriately set within a range that allows polymerization as a copolymer and maintains adhesion to the PET molded article. A practical specific upper limit is preferably 50 or less carbon atoms, more preferably 40 or less carbon atoms. The carbon number may also be 30 or less or 25 or less. If the alkyl group has too many carbon atoms, the copolymer may not have a suitable three-dimensional structure, or it may be difficult to set the polymerization conditions.

[0022] Specific examples of alkyl groups having 8 or more carbon atoms include decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl (stearyl), and docosyl (behenyl) groups.

[0023] The degree of polymerization of block (A) is 2 or more. The degree of polymerization of block (A) may be appropriately selected depending on the structure of the block copolymer and other factors, within a range in which adhesion to a PET molded article can be maintained. To improve adhesion to a PET molded article, the degree of polymerization of block (A) is preferably 7 or more, and may be 8 or more or 10 or more. The degree of polymerization of block (A) is preferably 1,000 or less, and may be 800 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0024] The molecular weight corresponding to block (A) is preferably 3,000 or more. By having a molecular weight corresponding to block (A) of 3,000 or more, stronger adhesion to a PET molded article can be achieved. The molecular weight corresponding to block (A) may be 4,000 or more or 5,000 or more. Alternatively, it may be 20,000 or less, 15,000 or less, 10,000 or less, or 8,000 or less.

[0025] These molecular weights are "Mw: weight average molecular weight" values that can be calculated in polystyrene equivalent from the results obtained by GPC. In some cases, the modifying copolymer is difficult to dissolve in a solvent, making it difficult to measure the molecular weight. In such cases, the molecular weights can be calculated using techniques such as elemental analysis, IR, and NMR.

[0026] The first polymer block (block (A)) is preferably a polymer of any one monomer (hereinafter referred to as "monomer (a)") selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, which has an alkyl group having 8 or more carbon atoms in its side chain. In other words, the block copolymer preferably contains a structural unit (A) derived from monomer (a).

[0027] As the monomer (a), commercially available products or appropriately synthesized products can be used.

[0028] As the (meth)acrylate having an alkyl group having 8 or more carbon atoms, a (meth)acrylate obtained by reacting a (meth)acrylate with an alcohol having 8 or more carbon atoms can be used.

[0029] As the (meth)acrylamide having an alkyl group having 8 or more carbon atoms, an alkyl(meth)acrylamide obtained by reacting a (meth)acrylate with an alkylamine having 8 or more carbon atoms can be used.

[0030] As the vinyl ether having an alkyl group having 8 or more carbon atoms, an alkyl vinyl ether obtained by reacting methyl vinyl ether with an alcohol having 8 or more carbon atoms, etc. can be used.

[0031] As the vinyl ester having an alkyl group having 8 or more carbon atoms, a vinyl carboxylate obtained by reacting vinyl acetate with an aliphatic carboxylic acid having 9 or more carbon atoms can be used.

[0032] The α-olefin having an alkyl group having 8 or more carbon atoms may be an α-olefin obtained by decarbonylation of an aliphatic carboxylic acid having 11 or more carbon atoms.

[0033] As the substituted styrene having an alkyl group having 8 or more carbon atoms, an alkylstyrene obtained by reacting a Grignard reagent of a halogenated styrene with an alkyl halide having 8 or more carbon atoms can be used.

[0034] In this specification, "(meth)acrylate" refers to both acrylate and methacrylate. Similarly, "(meth)acrylamide" refers to both acrylamide and methacrylamide.

[0035] Specific examples of the monomer (a) include dodecyl acrylate (lauryl acrylate), dodecyl methacrylate (lauryl methacrylate), octadecyl acrylate (stearyl acrylate), octadecyl methacrylate (stearyl methacrylate), docosyl acrylate (behenyl acrylate), docosyl methacrylate (behenyl methacrylate), and the like.

[0036] Other examples include N-tert-octylacrylamide, N-dodecylacrylamide, N-dodecylmethacrylamide, N-octadecylacrylamide, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, 1-tridecene, 1-pentadecene, and 4-n-octylstyrene.

[0037] Monomer (a) is preferably a (meth)acrylate or α-olefin monomer having an alkyl group with 8 or more carbon atoms in the side chain, and more preferably a (meth)acrylate having an alkyl group with 8 or more carbon atoms in the side chain.

[0038] From the viewpoints of ease of obtaining the monomer (a), ease of controlling the polymerization conditions, ease of interaction between alkyl groups having 8 or more carbon atoms, etc., the block (A) is preferably a (meth)acrylate having an alkyl group having 8 or more carbon atoms, or a polymer of an α-olefin having an alkyl group having 8 or more carbon atoms.

[0039] Specifically, the block (A) is preferably represented by the following general formula (A-1) or (A-2), and more preferably represented by general formula (A-1).

[0040] [ka]

[0041] In general formulas (A-1) and (A-2), R a1 represents a hydrogen atom or a methyl group.

[0042] In general formulas (A-1) and (A-2), R a2 represents an alkyl group having 8 or more carbon atoms. a2 is preferably a linear alkyl group. a2 The number of carbon atoms in the alkyl group represented by the formula (I) is preferably 10 or more, more preferably 12 or more, and even more preferably 14 or more. The upper limit can be 50 or less, 40 or less, 30 or less, 28 or less, or 25 or less, for example.

[0043] In general formulas (A-1) and (A-2), m is an integer of 2 or greater. m is preferably 7 or greater, more preferably 8 or greater, or even 10 or greater. m is preferably 1,000 or less, and may be 800 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0044] [Second Polymer Block] The second polymer block (hereinafter referred to as "block (B)") is a repeating structural unit having a functional group. This block (B) is the part that exhibits functionality according to the purpose of modification.

[0045] Here, the functional group is a group that exists in large numbers in the block copolymer even after copolymerization, thereby imparting functionality to the PET molded article. Examples of functionality imparted to the PET molded article include adhesiveness, hydrophilicity, dyeability, ion conductivity, metal adsorption ability, metal support properties, and plating adhesion. The functional group possessed by block (B) refers to a group that can impart these functionalities. The functional group is appropriately selected in consideration of the desired function and the ease of polymerization of the copolymer, and the constituent units of block (B) may have two or more functional groups.

[0046] Since the functionality derived from the functional group is easily manifested on the surface of the PET molded article and the modifying effect is large, those having a functional group in the portion that will become the side chain of block (B) are preferred. In this case, the functional group (particularly a polar group) in the side chain is directly bonded to the portion that will become the main chain of block (B) or is bonded via a linking group (ester bond, amide bond, ether bond, benzene ring, etc.). In this case, the portion that will become the main chain of block (B) has little effect on the modification, so the structure of the main chain is not particularly limited.

[0047] The degree of polymerization of block (B) is an integer of 2 or more. The degree of polymerization of block (B) is determined appropriately depending on the structure of the block copolymer. The degree of polymerization of block (B) is preferably 2 to 1,000. To achieve a more stable modifying effect, it is more preferably 5 or more, or 10 or more. It may also be 20 or more, 30 or more, or 40 or more. The degree of polymerization of block (B) may also be 800 or less, 500 or less, 300 or less, 100 or less, or 60 or less.

[0048] The molecular weight corresponding to block (B) is preferably 500 or more. By having a molecular weight corresponding to block (B) of 500 or more, a copolymer with even better adhesiveness to other materials can be obtained. The molecular weight corresponding to block (B) is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. It may also be 20,000 or less, 15,000 or less, or 12,000 or less.

[0049] The functional group contained in block (B) is preferably a polar group. A polar group is a polar atomic group that, when present in a polymer using a monomer having such a group, forms a polar structure within the polymer. The polar groups are advantageous in that the properties of the resulting modified PET molded article are significantly different from those of ordinary PET molded articles (PET molded articles before modification). In particular, the polar groups in block (B) enable the production of modified PET molded articles with excellent adhesiveness to other materials.

[0050] Representative polar groups include an amino group, an ammonium group, a carboxyl group, a hydroxyl group, a sulfonic acid group, an alkoxy group, an oxiranyl group, an oxyalkylene group, a carbonyl group, an ether group, a sulfonyl group, an ester group, and an amide group.

[0051] Block (B) preferably has a polar group in the side chain, and is preferably a repeating structural unit having an amino group in the side chain. Also, block (B) preferably has a repeating structural unit having an oxyalkylene group in the side chain. Also, block (B) preferably has a repeating structural unit having a carboxyl group in the side chain.

[0052] For example, block (B) can be a polymer of any monomer (hereinafter referred to as "monomer (b)") having a polar group in its side chain and selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene. In other words, the block copolymer can contain a structural unit (B) derived from monomer (b). Block (B) can also be a (meth)acrylic acid polymer.

[0053] As the monomer (b), commercially available products or appropriately synthesized products can be used.

[0054] Block (B) can be a polymer of a monomer having an amino group, in which case monomer (b) is a monomer having an amino group, preferably a monomer having an amino group in its side chain.

[0055] Here, the amino group may be unsubstituted or may have a substituent. Examples of the substituent on the amino group include an alkyl group, and the alkyl group can be an unsubstituted alkyl group or a substituted alkyl group such as a carboxyalkyl group (—R—COOH). The amino group has the general formula "-NR x1 R x2 (However, R x1 and R x2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a carboxyalkyl group having 1 to 4 carbon atoms). Examples of such amino groups include -NH, -N(CH), -N(CH), -NH(tert-CH), and -N(CHCOOH).

[0056] Block (B) can be a polymer of a monomer having an oxyalkylene group. In this case, monomer (b) can be a monomer having an oxyalkylene group, and preferably a monomer having an oxyalkylene group in its side chain.

[0057] The oxyalkylene group is "-(C p H 2p It is a divalent group represented by the formula (—O)— (p is an integer of 1 or more). When the monomer (b) has an oxyalkylene group, it preferably has a group represented by the following general formula (Y).

[0058] -(C p H 2p -O) q -R y1 ····(Y) (In the general formula (Y), p is an integer of 1 to 10, q is an integer of 1 to 10, R y1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0059] More preferably, in the general formula (Y), p is an integer of 1 to 5, q is an integer of 2 to 10, and R y1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. More preferably, p is an integer of 1 to 2, q is an integer of 2 to 10, and R y1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

[0060] Specific examples of the monomer (b) include monomers having an amino group, such as 2-(dimethylamino)ethyl methacrylate (DMAEMA), 2-(dimethylamino)ethyl acrylate (DMAEA), 2-(diethylamino)ethyl methacrylate (DEAEMA), 2-(diethylamino)ethyl acrylate (DEAEA), 2-(tert-butylamino)ethyl methacrylate (TBAEMA), N,N-dimethylacrylamide (DMAA), N,N-dimethylaminopropyl acrylamide (DMAPAA), and N,N-diethylacrylamide (DEAA).

[0061] Further examples include monomers having an amino group, such as N-[3-(dimethylamino)propyl]acrylamide, N-[2-(dimethylamino)ethyl]acrylamide, N-[2-(diethylamino)ethyl]acrylamide, 2-(vinyloxy)ethanamine, 3-amino-1-propene (allylamine), N,N-diethylallylamine, N-allyl-N-tert-butylamine, 3-amino-2-methyl-1-propene (2-methylallylamine), N,N-dimethylallylamine, N,N-dimethylallylamine, 4-aminostyrene, 3-aminostyrene, N,N-dimethyl-4-vinylbenzene-1-amine, 4-(aminomethyl)styrene, 4-[N-(methylaminoethyl)aminomethyl]styrene, and N,N-dimethylvinylbenzylamine.

[0062] Also, as the monomer (b), methoxy-polyethylene glycol-acrylate (CH2=CH(CO)O(CH2-CH2-O-) q CH3) (q=2~10), ethoxy-polyethylene glycol-acrylate (CH2=CH(CO)O(CH2-CH2-O-) q C2H5) (p=2, q=2-10), polyethylene glycol monoacrylate (CH2=CH(CO)O(CH2-CH2-O-) q Examples of suitable monomers include monomers having an oxyalkylene group, such as di(ethylene glycol) ethyl ether acrylate (CH2=CH(CO)O(CH2-CH2-O-)2C2H5, Diethylen Glycol Monoethyl Ether Acrylate, DEEA) and deca(ethylene glycol) ethyl ether acrylate (CH2=CH(CO)O(CH2-CH2-O-) 10 Examples include monomers having an oxyalkylene group such as C2H5).

[0063] Further examples include monomers having an oxyalkylene group, such as ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, and tetraethylene glycol methyl vinyl ether.

[0064] Examples of monomers having a sulfonic acid group include vinyl sulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, ATBS (Acrylamide Tertiary Butyl Sulfonic Acid), and its sodium salt ATBSNa. Examples of monomers having a hydroxyl group or a carboxyl group include acrylic acid and its sodium salt, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, etc. Furthermore, the block (B) may have a structure in which a polymer of a monomer having a reactive group such as an oxiranyl group on the side chain (hereinafter referred to as "monomer (b1)") has reacted with an amine.

[0065] Specific examples of the monomer (b1) include glycidyl acrylate and glycidyl methacrylate.

[0066] The block (B) can have, for example, a structure represented by the following general formulas (B-1) to (B-4).

[0067] [ka]

[0068] In the general formulae (B-1) to (B-4), R b1 represents a hydrogen atom or a methyl group.

[0069] In the general formulae (B-1) to (B-4), R L represents a single bond or an alkylene group, and is preferably a single bond or an alkylene group having 1 to 4 carbon atoms.

[0070] The alkylene group may be unsubstituted or may have a substituent. Examples of the alkylene group having a substituent include an alkylene group substituted with a hydroxy group or a hydroxyalkyl group.

[0071] In the general formulae (B-1) to (B-4), R b2represents any one selected from the group consisting of a hydrogen atom, an alkyl group, an amino group, an ammonium group, a carboxyl group, a hydroxyl group, a sulfonic acid group, an alkoxy group, an oxiranyl group, and a group represented by the above general formula (Y). R b2 is preferably any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an amino group, and a group represented by the above general formula (Y), and more preferably any one selected from the group consisting of a hydrogen atom, an amino group, and a group represented by the above general formula (Y). The preferred embodiments of the amino group and the group represented by general formula (Y) are as described above.

[0072] In general formula (B-2), R b3 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0073] In general formulas (B-1) to (B-4), n is an integer of 2 or more. n is preferably 8 or more, and may be 10 or more, 20 or more, 30 or more, or 40 or more. Furthermore, n is preferably 1,000 or less, and may be 800 or less, 500 or less, 300 or less, 100 or less, or 60 or less.

[0074] The block (B) represented by general formula (B-1) can be, for example, a polymer of an aminoalkyl(meth)acrylate. The aminoalkyl(meth)acrylate may be a commercially available product or a product obtained by reacting a (meth)acrylate with an alkanolamine.

[0075] Furthermore, the block (B) represented by general formula (B-1) can be, for example, a polymer of polyalkylene glycol mono(meth)acrylate or alkoxypolyalkylene glycol mono(meth)acrylate. The polyalkylene glycol mono(meth)acrylate or alkoxypolyalkylene glycol mono(meth)acrylate can be commercially available or one obtained by reacting a (meth)acrylate with a polyalkylene glycol or a polyalkylene glycol monoalkyl ether.

[0076] The block (B) represented by general formula (B-2) can be, for example, a polymer of alkyl(meth)acrylamide or aminoalkyl(meth)acrylamide. The alkyl(meth)acrylamide may be commercially available or may be obtained by reacting (meth)acrylate with an alkylamine. The aminoalkyl(meth)acrylamide may be commercially available or may be obtained by reacting (meth)acrylate with an alkylenediamine.

[0077] The block (B) represented by general formula (B-3) can be, for example, a polymer of an aminoalkyl vinyl ether. The aminoalkyl vinyl ether can be a commercially available product or a product obtained by reacting methyl vinyl ether with an alkanolamine.

[0078] Furthermore, the block (B) represented by general formula (B-3) can be, for example, a polymer of polyalkylene glycol monovinyl ether or alkoxypolyalkylene glycol monovinyl ether. The polyalkylene glycol monovinyl ether or alkoxypolyalkylene glycol monovinyl ether can be commercially available products or products obtained by reacting methyl vinyl ether with polyalkylene glycol or polyalkylene glycol monoalkyl ether.

[0079] The block (B) represented by general formula (B-4) can be, for example, a polymer of an aminocarboxylic acid vinyl ester. The aminocarboxylic acid vinyl ester can be a commercially available product or a product obtained by reacting vinyl acetate with an aminoalkylcarboxylic acid.

[0080] Moreover, the block (B) can have a structure represented by the following general formulas (B-5) to (B-7).

[0081] [ka]

[0082] In general formulae (B-5) to (B-7), R b4 represents a hydrogen atom or a methyl group.

[0083] In general formulae (B-5) to (B-7), R L represents a single bond or an alkylene group, and is preferably a single bond or an alkylene group having 1 to 4 carbon atoms.

[0084] The alkylene group may be unsubstituted or may have a substituent. Examples of the alkylene group having a substituent include an alkylene group substituted with a hydroxy group or a hydroxyalkyl group.

[0085] In general formulae (B-5) to (B-7), R b5 represents any one selected from the group consisting of an amino group, an ammonium group, a carboxyl group, a hydroxyl group, a sulfonic acid group, an alkoxy group, an oxiranyl group, and a group represented by general formula (Y). R b5 is preferably any one selected from the group consisting of an amino group and a group represented by the above general formula (Y), and more preferably an amino group. The preferred embodiments of the amino group and the group represented by the general formula (Y) are as described above.

[0086] In general formulas (B-5) to (B-7), n is an integer of 2 or greater. n may be 5 or greater, 10 or greater, 20 or greater, 30 or greater, or 40 or greater. n is preferably 1,000 or less, and may be 800 or less, 500 or less, 300 or less, 100 or less, or 60 or less.

[0087] The block (B) represented by general formula (B-6) can be, for example, a polymer of allylamine. The allylamine can be a commercially available product or one obtained by reacting allyl alcohol with ammonia or an alkylamine.

[0088] Furthermore, the block (B) represented by general formula (B-6) can be, for example, a polymer of a polyalkylene glycol monoallyl ether or an alkoxypolyalkylene glycol monoallyl ether. The polyalkylene glycol monoallyl ether or alkoxypolyalkylene glycol monoallyl ether can be a commercially available product, or a product obtained by reacting an allyl halide with a polyalkylene glycol or a polyalkylene glycol monoalkyl ether.

[0089] The block (B) represented by general formula (B-7) can be, for example, a polymer of aminostyrene or aminoalkylstyrene. The aminoalkylstyrene can be a commercially available product or one obtained by reacting a vinylbenzyl halide with an alkylamine.

[0090] The block (B) represented by general formula (B-7) can be, for example, a polymer of polyalkylene glycol monovinylbenzyl ether or alkoxypolyalkylene glycol monovinylbenzyl ether. The polyalkylene glycol monovinylbenzyl ether or alkoxypolyalkylene glycol monovinylbenzyl ether can be a commercially available product, or a product obtained by reacting a vinylbenzyl halide with a polyalkylene glycol or a polyalkylene glycol monoalkyl ether.

[0091] Block (B) is preferably represented by general formula (B-1) or general formula (B-2), more preferably general formula (B-1), in view of the ease of obtaining the raw material monomers and the ease of controlling the polymerization conditions.

[0092] [Side chain crystalline block copolymer] The side chain crystalline block copolymer comprises a first polymer block (block (A)) having an alkyl group with 8 or more carbon atoms in the side chain, and a second polymer block (block (B)) having a functional group. By forming a block copolymer, each function can be more easily exerted. This block copolymer may be composed of block (A) and block (B), and may further contain other structural units as long as the object of the present invention is not impaired. The side-chain crystalline block copolymer is preferably composed essentially of block (A) and block (B), and the total content of block (A) and block (B) in the side-chain crystalline block copolymer may be 95% by mass or more, or 98% by mass or more. The block copolymer may also be a diblock copolymer, a triblock copolymer, or the like.

[0093] In the side-chain crystalline block copolymer, the molecular weight of block (A) is preferably 3,000 or more and the molecular weight of block (B) is preferably 500 or more. Such molecular weights allow stable adhesion between the PET molded article and the block copolymer. More preferably, the molecular weight of block (A) is 5,000 or more and the molecular weight of block (B) is 1,000 or more, and even more preferably, the molecular weight of block (A) is 5,000 or more and the molecular weight of block (B) is 5,000 or more.

[0094] The side chain crystalline block copolymer is more preferably any of the following (p1) to (p3). (p1) A block copolymer containing a block (A) derived from a (meth)acrylate having an alkyl group having 8 or more carbon atoms and a block (B) derived from a (meth)acrylate having an amino group. (p2) A block copolymer comprising a block (A) derived from a (meth)acrylate having an alkyl group having 8 or more carbon atoms and a block (B) derived from a (meth)acrylate having a group represented by the above general formula (Y). (p3) A block copolymer comprising a block (A) derived from a (meth)acrylate having an alkyl group having 8 or more carbon atoms and a block (B) derived from (meth)acrylic acid.

[0095] One preferred block copolymer is a block copolymer containing a block (A) represented by the above general formula (A-1) and a block (B) represented by the above general formula (B-1). The use of such a block copolymer ensures strong adhesion between the block (A) and the PET molded article, making it easier to strongly exhibit the functions of the block (B).

[0096] More specifically, the following can be used as the block copolymer:

[0097] [ka]

[0098] The polymerization method for the block copolymer is not particularly limited, and polymerization can be performed by known techniques such as various living polymerization methods (radical, anionic, cationic). Examples of living radical polymerization methods that can be used include the NMP method, the ATRP method, and the RAFT method.

[0099] For example, a monomer (a) mixed solution preparation step is performed in which monomer (a) is mixed with a polymerization solvent and an initiator to prepare a monomer (a) mixed solution. Next, the monomer (a) mixed solution prepared in this mixed solution preparation step is subjected to a monomer (a) polymerization step based on the initiator's polymerization mechanism, such as living radical polymerization, in a nitrogen atmosphere or the like, while being appropriately stirred in a reactor at an appropriate polymerization temperature (e.g., approximately 90 to 120°C), to obtain a monomer (a) polymer. Furthermore, a monomer (b) polymerization step is performed in which monomer (b) is mixed with the solution containing the monomer (a) polymer, and monomer (b) is further polymerized by radicals or the like in the solution. This allows for the production of a block copolymer containing a block (A) derived from monomer (a) and a block (B) derived from monomer (b). The order in which monomer (a) and monomer (b) are polymerized can be varied depending on the type and molecular weight of the monomers to be polymerized, the polymerization conditions, etc.

[0100] When another monomer is contained, it may be added as a third monomer to the monomer (a) and the monomer (b) and polymerized.

[0101] Alternatively, a precursor polymer may be synthesized by polymerizing the monomer (a) with a monomer (b1) having a reactive group such as an oxiranyl group on its side chain, and then reacting the precursor polymer with an amine or the like to obtain a block copolymer.

[0102] Specifically, similar to the above, monomer (a) is mixed with an initiator in a polymerization solvent, and the mixture is stirred in a reactor at an appropriate polymerization temperature (e.g., about 90 to 120°C) under a nitrogen atmosphere or the like while undergoing a monomer (a) polymerization step based on the initiator's polymerization mechanism, such as living radical polymerization, to obtain a monomer (a) block polymer. Monomer (b1) (e.g., a monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, each having an oxiranyl group) is then mixed into the solution containing the monomer (a) block polymer, and a monomer (b1) polymerization step is performed to further polymerize monomer (b1) using radicals or the like in the solution. This results in a solution containing a precursor polymer having block (A) derived from monomer (a) and block (B1) derived from monomer (b1). Next, when this precursor polymer is reacted with iminodiacetic acid, the oxiranyl group reacts with the iminodiacetic acid, resulting in a block copolymer (e.g., copolymer (IX) above) having an amine structure derived from iminodiacetic acid (a structure having a carboxyalkyl group-substituted amino group in the side chain).

[0103] [Block copolymer solution] In the present invention, a copolymer solution in which a side-chain crystalline block copolymer is dissolved in a solvent is used. By using the copolymer solution, it is possible to adjust the viscosity and concentration as desired, and it is easy to impart desired functionality, such as adhesiveness, to a desired range of the PET molded article.

[0104] In the present application, the concept of a block copolymer solution includes not only a homogeneous solution in which the block copolymer is completely dissolved in a solvent, but also a suspension or dispersion. Depending on the structure of the block copolymer, it may be difficult to completely dissolve the block copolymer in a solvent. Therefore, a suspension or dispersion in which the block copolymer is dispersed or suspended in a solvent may also be used.

[0105] (solvent) Examples of solvents for the copolymer solution include aprotic polar solvents such as ester solvents such as butyl acetate, octyl acetate, methyl benzoate, ethyl benzoate, octyl benzoate, dimethyl phthalate, diethyl phthalate, and dioctyl phthalate; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide; ether solvents such as tetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, diethylene glycol methyl ether, anisole, and methylanisole; ketone solvents such as methyl isobutyl ketone, cyclohexanone, and acetophenone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile; and phosphoric acid amide solvents such as hexamethylphosphoric acid triamide.

[0106] The solvent for the copolymer solution may be a protic solvent such as ethanol, isopropyl alcohol, butanol, ethylene glycol, glycerin, 2-methoxyethanol, or 2-ethoxyethanol.

[0107] Examples of solvents for the copolymer solution include aromatic hydrocarbon solvents such as toluene, xylene (o-xylene, m-xylene, p-xylene, and mixtures thereof), mesitylene, ethylbenzene, and cyclohexylbenzene; halogenated aromatic hydrocarbon compounds such as chlorobenzene, dichlorobenzene, trichlorobenzene, bromobenzene, and fluorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, cyclohexane, and decalin; halogenated aliphatic hydrocarbon solvents such as trichloromethane, tetrachloromethane, dichloroethane, trichloroethylene, tetrachloroethylene, chlorobutane, and tribromomethane; and non-polar solvents such as ether solvents such as dioxane and diethyl ether.

[0108] The solvent may be used alone or in a suitable mixture of two or more solvents.

[0109] The solvent for the copolymer solution preferably contains an aprotic polar solvent, and more preferably contains an ester solvent or an aprotic polar solvent with a dielectric constant of 30 or more. The solvent for the copolymer solution is further preferably (i) an ester solvent with a boiling point of 150°C or more at 1 atm, or (ii) an aprotic polar solvent with a dielectric constant of 30 or more.

[0110] By using such a solvent, a higher modification effect can be obtained. In the present application, "dielectric constant" means relative dielectric constant. The dielectric constant of a solvent can be appropriately determined from values described in literature such as "Solvent Handbook," "Chemical Handbook," "Solvent Pocket Book," and "CRC HANDBOOK OF CHEMISTRY AND PHYSICS 88TH EDITION." When a measured value is used, the value can be measured at 20 to 25°C using a commercially available dielectric constant meter.

[0111] The ester solvent or the aprotic polar solvent having a dielectric constant of 30 or more may be used alone or as a mixed solvent with other solvents. When a mixed solvent is used, it is preferable that these solvents are the main solvent, and the ester solvent or the aprotic polar solvent having a dielectric constant of 30 or more accounts for preferably 50% by volume or more of the total volume of the solvent, and may also account for 70% by volume or more, 80% by volume or more, 90% by volume or more, or 95% by volume or more.

[0112] The ester solvent may be an aliphatic ester compound (butyl acetate, octyl acetate, etc.) or an aromatic ester compound (benzoic acid esters such as methyl benzoate, ethyl benzoate, octyl benzoate, etc., or phthalic acid ester compounds such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate, etc.), but an aromatic ester compound is preferred, and a phthalic acid ester compound is more preferred.

[0113] Furthermore, as described below, when using an ester-based solvent, heating during contact with the PET molded body provides a greater modification effect. Therefore, the ester-based solvent preferably has a boiling point of 80°C or higher at 1 atm, with 100°C or higher, 120°C or higher, 150°C or higher, 200°C or higher, and 220°C being more preferred in this order. If the boiling point of the ester-based solvent is lower than the temperature at which the copolymer solution contacts the PET molded body, refluxing may be used to prevent changes in the volume and concentration of the copolymer solution due to evaporation. However, using a solvent with a low boiling point can make it difficult to contact the copolymer solution with the PET molded body at the desired temperature, or may require improved refluxing, resulting in reduced operability. For this reason, the boiling point of the ester-based solvent is preferably within the above range. However, there is no particular need to set an upper limit on the boiling point.

[0114] Aprotic polar solvents with a dielectric constant of 30 or more (hereinafter, the numbers in parentheses represent the dielectric constant) include amide solvents such as N-methyl-2-pyrrolidone (32), N,N-dimethylacetamide (38), and N,N-dimethylformamide (38); sulfoxide solvents such as dimethyl sulfoxide (47); nitrile solvents such as acetonitrile (37); and phosphoric acid amide solvents such as hexamethylphosphoric acid triamide (31). Among these, sulfoxide solvents and / or amide solvents are preferred, and dimethyl sulfoxide and / or N-methyl-2-pyrrolidone are more preferred.

[0115] (concentration) The concentration of the block copolymer in the copolymer solution can be appropriately set depending on the type of block copolymer, the modification temperature, the amount of copolymer to be bonded, the thickness of the bonded film, the purpose of modification, etc. The concentration of the block copolymer in the copolymer solution is preferably 0.01 to 2.0% by mass. The lower limit of the block copolymer concentration is preferably 0.02% by mass or more, more preferably 0.05% by mass or more. If the block copolymer concentration is too low, the modifying effect on the PET molded article may be insufficient. The upper limit of the block copolymer concentration is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. It can also be 0.8% by mass or less, 0.6% by mass or less, or 0.5% by mass or less. Even if the block copolymer concentration is increased, the modifying effect on the PET molded article may saturate. Furthermore, if the block copolymer concentration is too high, micellization due to self-assembly of the block copolymer itself may occur, preventing the modification effect from being fully exerted.

[0116] An example of a copolymer solution for modifying polyethylene terephthalate is a solution containing a side-chain crystalline block copolymer and a solvent, wherein the side-chain crystalline block copolymer contains a block (A) derived from a (meth)acrylate having an alkyl group with 8 or more carbon atoms and a block (B) having a polar group in the side chain, the concentration of the side-chain crystalline block copolymer being 0.01 to 2.0 mass%, and the solvent containing the following (i) or (ii): (i) Ester solvents with a boiling point of 150°C or higher at 1 atm (ii) aprotic polar solvents with a dielectric constant of 30 or more

[0117] For example, a copolymer solution for modifying polyethylene terephthalate can be a solution containing a block copolymer including a block (A) derived from a (meth)acrylate having an alkyl group with 8 or more carbon atoms and a block (B) having a polar group in the side chain, and a solvent, wherein the solvent contains an ester-based solvent having a boiling point of 150°C or higher at 1 atm, and the concentration of the block copolymer is 0.01 to 2.0 mass% (hereinafter, this may be referred to as "copolymer solution (L1)").

[0118] By using the copolymer solution (L1), the polyethylene terephthalate molded article and the block copolymer can be more firmly bonded together.

[0119] In the copolymer solution (L1), the solvent is preferably an ester-based solvent containing an aromatic ester compound and having a boiling point of 220°C or higher at 1 atm, and more preferably an ester-based solvent containing a phthalate ester compound.

[0120] In the copolymer solution (L1), the block copolymer is preferably a block copolymer containing a block (A) derived from a (meth)acrylate having an alkyl group with 8 or more carbon atoms and a block (B) having an amino group, a group represented by the general formula (Y) above, or a carboxyl group on its side chain.More preferably, the block copolymer is a block copolymer containing a block (A) derived from a (meth)acrylate having an alkyl group with 8 or more carbon atoms and a block (B) derived from a (meth)acrylate having an amino group, a (meth)acrylate having a group represented by the general formula (Y) above, or (meth)acrylic acid.

[0121] Furthermore, as a copolymer solution for modifying polyethylene terephthalate, a solution containing a block copolymer including a block (A) derived from a (meth)acrylate having an alkyl group having 8 or more carbon atoms and a block (B) having a polar group in the side chain, and a solvent, wherein the solvent contains an aprotic polar solvent having a dielectric constant of 30 or more, and the concentration of the block copolymer is 0.01 to 2.0 mass % (hereinafter, sometimes referred to as "copolymer solution (L2)") can be used.

[0122] By using the copolymer solution (L2), the polyethylene terephthalate molded article and the block copolymer can be more firmly bonded together.

[0123] In the copolymer solution (L2), the solvent is preferably an aprotic polar solvent having a dielectric constant of 30 or more, including a sulfoxide-based solvent and / or an amide-based solvent, and more preferably an aprotic polar solvent having a dielectric constant of 30 or more, including dimethyl sulfoxide and / or N-methyl-2-pyrrolidone.

[0124] In the copolymer solution (L2), the block copolymer is preferably a block copolymer containing a block (A) derived from a (meth)acrylate having an alkyl group with 8 or more carbon atoms and a block (B) having an amino group, a group represented by the general formula (Y) above, or a carboxyl group on its side chain.More preferably, the block copolymer is a block copolymer containing a block (A) derived from a (meth)acrylate having an alkyl group with 8 or more carbon atoms and a block (B) derived from a (meth)acrylate having an amino group, a (meth)acrylate having a group represented by the general formula (Y) above, or (meth)acrylic acid.

[0125] [Polyethylene terephthalate (PET) molded body] A polyethylene terephthalate (PET) molded article is a molded article containing polyethylene terephthalate as a main component (e.g., containing 50% by mass or more), and is obtained by molding polyethylene terephthalate, its copolymers, mixtures of polyethylene terephthalate with other resins, etc. into any shape. This molded article may also contain appropriate functionality-imparting agents such as molding aids, pigments, and ultraviolet absorbers.

[0126] The form of the PET molded article is not particularly limited, and examples thereof include molded articles such as films, plates, particles, fibers, porous materials, etc. In the method for producing a modified PET molded article of the present invention, even if the substrate to be modified is a porous material, the copolymer solution can be infiltrated not only into the surface of the molded article, but also into the interior of the PET molded article, such as into the pores, thereby modifying the entire porous material.

[0127] [Contact process] The method for producing a modified PET molded article of the present invention includes a step of contacting a polyethylene terephthalate molded article with a copolymer solution containing a side-chain crystalline block copolymer and a solvent.

[0128] The method for contacting the copolymer solution with the PET molded article is not particularly limited, as long as it allows for the formation of a functional layer containing a block copolymer in the portion of the PET molded article to be modified. A method for contacting the portion of the PET molded article to be modified with the copolymer solution can be appropriately selected depending on the shape of the PET molded article, the extent of modification, etc. Examples of contact methods include dip coating, spin coating, applicator coating, slit coating, die coating, bar coating, screen printing, inkjet printing, gravure printing, spray coating, and pouring. One preferred contact method is immersing the PET molded article in the copolymer solution, as this allows for easy control of the copolymer solution at a predetermined temperature.

[0129] The temperature (modification temperature) at which the block copolymer is brought into contact with the PET molded article can be appropriately determined depending on the type of solvent in the copolymer solution, the shape of the PET molded article, the contact time, and the like.

[0130] When the solvent for the copolymer solution contains an ester-based solvent, the modification temperature is preferably 80°C or higher, more preferably 100°C or higher, 120°C or higher, and 130°C or higher. Ester-based solvents have a dielectric constant of approximately 5 to 10, and at room temperature, they are unlikely to erode the surface of the PET molded body, which may result in a long modification time or in insufficient modification effects. By setting the modification temperature at 80°C or higher, the surface of the PET molded body is more likely to loosen or swell, facilitating interaction between the block copolymer and the PET molded body, thereby achieving a more efficient modification effect. Furthermore, when the solvent for the copolymer solution contains an ester-based solvent, the modification temperature is preferably 200°C or lower, more preferably 190°C or lower, 180°C or lower, and 170°C or lower. If the modification temperature is too high, depending on the shape of the PET molded body, the PET molded body itself may undergo thermal degradation or deformation, resulting in a decrease in the strength of the PET molded body itself. Even when the reforming temperature is high, the influence of the temperature may be limited by shortening the contact time, thereby achieving reforming.

[0131] When the ester-based solvent contains (i) an ester-based solvent having a boiling point of 150°C or higher at 1 atm, it is preferable to bring the copolymer solution into contact with the PET molded article within the above-mentioned range of 80°C to 200°C (particularly, 120°C to 200°C).

[0132] In particular, when the ester solvent contains a phthalate ester compound, it is preferable to bring the copolymer solution into contact with the PET molded article within the above-mentioned range of 80°C to 200°C (particularly, 120°C to 200°C).

[0133] When the solvent for the copolymer solution contains an aprotic polar solvent with a dielectric constant of 30 or higher, the modification temperature is preferably 120°C or lower, with 100°C or lower, 90°C or lower, 80°C or lower, and 70°C or lower being more preferred in this order. Because aprotic polar solvents with a dielectric constant of 30 or higher tend to corrode the surface of PET molded articles, the higher the modification temperature, the greater the likelihood of a decrease in the strength of the PET molded article itself. While shortening the contact time can minimize the effect of temperature and suppress a decrease in the strength of the PET molded article itself, this can complicate the process, requiring more precise control of temperature and time. Setting the temperature at 120°C or lower allows for a simpler process while suppressing a decrease in the strength of the PET molded article itself. Furthermore, when the solvent for the copolymer solution contains an aprotic polar solvent with a dielectric constant of 30 or higher, the modification temperature is preferably 20°C or higher, with 25°C or higher and 30°C or higher being more preferred. If the modification temperature is too low, the surface of the PET molded article is less likely to loosen or swell, and the block copolymer and the PET molded article are less likely to interact with each other, so the lower the modification temperature, the more likely the modification effect will be insufficient.

[0134] In particular, when the aprotic polar solvent having a dielectric constant of 30 or more contains dimethyl sulfoxide and / or N-methyl-2-pyrrolidone, it is preferable to bring the copolymer solution into contact with the PET molded article within the above-mentioned range of 20°C to 120°C.

[0135] When the copolymer solution is brought into contact with the PET molded article at the predetermined temperature, the copolymer solution may be heated to the predetermined temperature beforehand. When the modification temperature is about room temperature (25°C) or higher, the PET molded article may be brought into contact with the copolymer solution at about room temperature and then heated to the predetermined temperature. After the contact at the predetermined temperature, the copolymer solution may be quickly removed, or the copolymer solution may be cooled or gradually cooled while still in contact with the PET molded article.

[0136] The treatment time for contacting the copolymer solution with the PET molded article can be determined appropriately depending on the contact method, the composition of the copolymer solution, the shape of the PET molded article, etc. For example, in a method of immersing a PET molded article in a copolymer solution, if the method is performed under conditions in which the reactivity between the block copolymer and the PET molded article is increased by, for example, increasing the modification temperature, the immersion time may be relatively short, such as 1 second or more, 10 seconds or more, or 30 seconds or more. Furthermore, to sufficiently form a functional layer, the immersion time may be 1 minute or more, 5 minutes or more. The immersion time may be longer, such as 60 minutes or less, or 40 minutes or less, as long as it does not cause deformation of the PET molded article. Furthermore, because the modification effect of contacting the block copolymer with the PET molded article saturates after a certain time, the immersion time may be 30 minutes or less, or 20 minutes or less, depending on conditions such as the modification temperature.

[0137] After the contact step is completed, the modified PET molded article may be used as it is, or may be further treated before use.

[0138] After the contact step, depending on the intended use of the modified PET molded body, a solvent removal step may be carried out to remove the solvent from the coating of the copolymer solution applied to the PET molded body, or further processing may be carried out directly. The method for removing the solvent may be drying at about room temperature in a well-ventilated environment, or drying under reduced pressure or drying by heating, etc. These drying methods may be used in combination. Alternatively, the copolymer may be washed with a solvent that is compatible with the solvent of the copolymer solution and has a lower boiling point, and then dried.

[0139] <Modified polyethylene terephthalate molded body> The present invention relates to a modified polyethylene terephthalate molded article (hereinafter sometimes referred to as the "modified PET molded article of the present invention") having a polyethylene terephthalate molded article and a functional layer containing a side-chain crystalline block copolymer formed on at least a portion of the surface of the molded article, wherein the side-chain crystalline block copolymer contains a first polymer block that is a repeating structural unit having an alkyl group having 8 or more carbon atoms in its side chain, and a second polymer block that is a repeating structural unit having a functional group.

[0140] The modified PET molded article of the present invention has a functional layer containing a block copolymer on at least a part of the surface of the PET molded article, and therefore is endowed with functionality due to the block copolymer.

[0141] The modified PET molded article of the present invention can be obtained, for example, by the above-mentioned method for producing the modified PET molded article of the present invention. The PET molded article and side-chain crystalline block copolymer constituting the PET molded article of the present invention are the same as those used in the method for producing the modified PET molded article of the present invention, and preferred embodiments are also the same.

[0142] As described above, the PET molded article can be formed into a film, plate, particle, fiber, porous material, or the like.

[0143] As described above, examples of functional groups in block (B) of the block copolymer include polar groups such as amino, ammonium, carboxyl, hydroxyl, sulfonic acid, alkoxy, oxiranyl, oxyalkylene, carbonyl, ether, sulfonyl, ester, and amide groups. It is known that the presence of polar groups on the surface can enhance functionality such as hydrophilicity and adhesiveness. By utilizing the production method of the present invention to modify the surface of a PET molded article with a block copolymer containing block (B) having a polar group as described above, strong adhesion between the block copolymer and the PET molded article can be achieved, resulting in a modified PET molded article with excellent functionality such as hydrophilicity, adhesiveness, dyeability, and metal ion adsorption.

[0144] Specifically, by modifying the surface of a PET molded article with a block copolymer containing a block (B) having an amino group, the modified PET molded article has amino groups on its surface, which gives it functionalities such as hydrophilicity, adhesiveness, dyeability, and metal ion adsorption.

[0145] By modifying the surface of a PET molded article with a block copolymer containing a block (B) having an oxyalkylene group, the modified PET molded article has oxyalkylene groups on the surface, which gives the modified PET molded article functionality such as hydrophilicity and adhesiveness.

[0146] By modifying the surface of a PET molded article with a block copolymer containing a carboxyl group-containing block (B), the modified PET molded article will have carboxyl groups on its surface, which will give the modified PET molded article functionality such as adhesiveness.

[0147] The functional group of block (B) of the block copolymer is preferably any one selected from the group consisting of an amino group, an ammonium group, a carboxyl group, a hydroxyl group, a sulfonic acid group, and an oxiranyl group, and more preferably an amino group, a carboxyl group, or an oxyalkylene group.

[0148] In the modified PET molded article, the block copolymer preferably contains a block (B) having an amino group, a carboxyl group or an oxyalkylene group in the side chain, and more preferably the following (p1) to (p3). (p1) A block copolymer comprising a block (A) derived from a (meth)acrylate having an alkyl group having 8 or more carbon atoms and a block (B) derived from a (meth)acrylate having an amino group. (p2) A block copolymer comprising a block (A) derived from a (meth)acrylate having an alkyl group having 8 or more carbon atoms and a block (B) derived from a (meth)acrylate having a group represented by the above general formula (Y). (p3) A block copolymer comprising a block (A) derived from a (meth)acrylate having an alkyl group having 8 or more carbon atoms and a block (B) derived from (meth)acrylic acid.

[0149] In the block copolymer constituting the modified PET molded article, the molecular weight of the block (A) is preferably 3,000 or more, and the molecular weight of the block (B) is preferably 500 or more. Such molecular weights allow for stable adhesion between the PET molded article and the block copolymer. More preferably, the molecular weight of the block (A) is 5,000 or more, and the molecular weight of the block (B) is 1,000 or more, and even more preferably, the molecular weight of the block (A) is 5,000 or more, and the molecular weight of the block (B) is 5,000 or more.

[0150] The functional layer containing the side-chain crystalline block copolymer may be formed in a region where the functionality of the side-chain crystalline block copolymer is required, and the range may be adjusted appropriately depending on the intended use of the modified PET molded article of the present invention. The functional layer may be formed on the entire surface of the PET molded article, or may be formed on the surface of the PET molded article in the form of a layer, spots, stripes, etc. Furthermore, if the PET molded article is a porous material such as a porous membrane, the functional layer may be formed not only on the surface but also within the pores.

[0151] Whether the molded article is the product of the present invention can be confirmed by analyzing the components of each layer using FT-IR or by analyzing the components of a cut surface.

[0152] In the modified PET molded article of the present invention, the functional layer may contain components other than the block copolymer. For example, the functional layer may contain a solvent. As described above, the modified PET molded article of the present invention can be produced by the method for producing a modified PET molded article of the present invention, in which a copolymer solution is brought into contact with the PET molded article. After contacting the copolymer solution with the PET molded article, the solvent of the copolymer solution applied to the PET molded article may be used without being removed, or even after solvent removal, the solvent may not be completely removed and may remain.

[0153] For example, the modified PET molded article of the present invention can be a molded article with excellent adhesiveness, and can also be a molded article with a peel strength on the surface of the functional layer of 0.1 N / mm or more, 0.5 N / mm or more, 0.7 N / mm or more, or 1.0 N / mm or more. The peel strength can be calculated by the T-peel test described below, and can be calculated as the maximum test force divided by the length of the test piece in the width direction. Furthermore, by adjusting the modification temperature, etc., a molded article with a peel strength on the surface of the functional layer of 5.0 N / mm or less, or 3.0 N / mm or less, can be obtained.

[0154] The modified PET molded article of the present invention has the properties of a side-chain crystalline block copolymer, which can be used for the conventional applications of PET molded articles, and is expected to be used in a wider range of applications by taking advantage of its modified properties.

[0155] Furthermore, even if the surface of a PET molded article is modified with a block copolymer, if the adhesion between the block copolymer and the PET molded article is weak, it is thought to be difficult to fully exhibit the functionality based on block (B) of the block copolymer. By using the production method of the present invention, it is possible to strongly bond the PET molded article and the block copolymer, and to obtain a modified PET molded article with excellent surface properties based on block (B).

[0156] The adhesive strength between a PET molded article and a block copolymer can be measured by peel strength. One preferred modified PET molded article of the present invention is a modified PET molded article (hereinafter sometimes referred to as modified molded article (M1)) that has a polyethylene terephthalate molded article and a functional layer formed on at least a portion of the surface of the molded article, the functional layer comprising a side-chain crystalline block copolymer, the side-chain crystalline block copolymer comprising a first polymer block (block (A)) that is a polymer of a monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, each having an alkyl group having 8 or more carbon atoms, and a second polymer block (block (B)) that is a repetition of a structural unit having a polar group in the side chain, the functional layer having a peel strength of 0.5 N / mm or more.

[0157] The modified molded product (M1) has a structure such that it can fully exhibit the functionality based on the block (B) of the block copolymer. In the modified molded product (M1), the peel strength of the functional layer is preferably 0.7 N / mm or more, more preferably 1.0 N / mm or more.

[0158] Furthermore, the strength of adhesion between a PET molded article and a block copolymer can be measured by the surface condition of the modified molded article after contacting the modified molded article with a good solvent for the block copolymer. The modified PET molded article of the present invention can be such that, even after contacting the modified PET molded article with a good solvent for the block copolymer, the block copolymer does not detach, and a portion containing the block copolymer remains on the surface. For example, even after contacting the modified PET molded article with butyl acetate at 55°C (e.g., for 1 minute), the block copolymer does not detach, and a portion containing the block copolymer remains on the surface. [Example]

[0159] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not changed.

[0160] <Evaluation> For gel permeation chromatography (GPC) measurements, HLC-8320GPC, EcoSEC (manufactured by Tosoh Corporation) was used. The IR spectrum was measured using Spectrum Two (manufactured by PerkinElmer Japan Co., Ltd.).

[0161] <Evaluation of adhesiveness of modified PET film> A T-peel test was performed in accordance with JIS K6854-3 (1999), and the peel strength was calculated to evaluate the adhesiveness. The test equipment used was a small desktop testing machine, EZ-testEZ-LX, manufactured by Shimadzu Corporation. The test specimens were two sheets of PET film (modified PET film) modified under the same conditions, bonded together using a cyanoacrylate adhesive (product name: Aron Alpha (registered trademark) 201, manufactured by Toagosei Co., Ltd.) (width: 12.5 mm, length of adhesive portion: 75 mm, length of non-adhesive portion: 25 mm) (see Figure 1(a)).

[0162] (peel test) The test was carried out in a constant temperature and humidity room at 25°C, 1 atmosphere, and 50% humidity. The non-adhesive portions of the test pieces were arranged in a T-shape, and each piece was gripped by the gripping tool of the testing device and pulled apart at 10 mm / min to measure the adhesive strength. Three to eight tests were carried out under each condition.

[0163] The peel strength [N / mm] was calculated by dividing the maximum test force [N] by the width [mm] of the test piece. As shown in Figure 1(b), the results for the first 12.5 mm of each peel test were cut out, and the maximum test force was calculated from the remaining results. This maximum test force was used to calculate the peel strength. In addition, if the test piece began to break immediately after the start of the test (within a stroke of 0 to 12.5 mm) due to strong adhesion, the maximum test force calculated from all data was used to calculate the peel strength. The peel strength was calculated as the average of all tests, regardless of whether the modified PET film itself broke during the peel test.

[0164] The evaluation results of the adhesiveness of the modified films are shown in Figures 3 to 10. In Figures 3 to 10, the white columns indicate that the modified PET film itself did not break during the peel test and all of the test pieces peeled off, while the black columns indicate that the test pieces also include those in which the modified PET film itself broke during the peel test. Details of the modification conditions and evaluation results for each modified film will be described later.

[0165] <Production of Side Chain Crystalline Block Copolymer (SCCBC)> [reagent] Stearyl acrylate (STA) was used as monomer (a), and 2-(tert-butylamino)ethyl methacrylate (TBAEMA) was used as monomer (b). These monomers were used after removing the stabilizers using Inhibitor Remover (Sigma-Aldrich). BlocBuilder (registered trademark) MA (manufactured by Arkema) was used as the polymerization initiator.

[0166] [Manufacturing] Stearyl acrylate and 2-(tert-butylamino)ethyl methacrylate were polymerized by living radical polymerization (NMP method) according to the following polymerization scheme. After the polymerization was terminated, the product was reprecipitated in methanol and dried in vacuo to obtain block copolymer (1) (STA-TBAEMA).

[0167] [ka]

[0168] The IR spectrum of the resulting block copolymer (1) showed absorption peaks due to the C=O of the ester, the CH stretching vibration of the alkyl chain of STA, and the CH stretching vibration of TBAEMA, but no absorption peaks due to vinyl bonds. This indicated that the polymerization of the block copolymer was successful.

[0169] Furthermore, the molecular weights of the block copolymer (1) were estimated from GPC, and the Mw (weight average molecular weight g / mol) of STA was 8,000, and the Mw of TBAEMA (weight average molecular weight g / mol) was 8,000.

[0170] <Manufacturing modified PET film> [Preparation of PET molding] As the PET molded article, a PET film (Lumirror (registered trademark) T60, film thickness 250 μm, manufactured by Toray Industries, Inc.) was cut into a width of 12.5 mm and a length of 100 mm. The cut PET film was washed with acetone and dried before use.

[0171] [Preparation of copolymer solution (SCCBC solution)] As shown in Table 1, solutions (S1) to (S7) having the compositions shown in Table 1 were obtained by dissolving the block copolymer (1) in a solvent.

[0172] [Table 1]

[0173] [Examples 1 to 5, Comparative Examples 1 to 4] The PET film was immersed in the heated solution (s1) for 10 minutes. The PET film was then removed from the solution (s1) and immersed in butyl acetate at 25°C, stirred and washed for 1 minute, and air-dried for 1 day to obtain a modified PET film. The solution temperature (modification temperature) in each example is as shown in Table 2. The PET film was used as is without modification in Comparative Example 1. Furthermore, treatment was carried out using the solutions or solvents shown in Table 2 under the modification conditions shown in Table 2 to obtain comparative PET films of Comparative Examples 2 to 4.

[0174] [Table 2]

[0175] (Confirmation of SCCBC on PET film) Figure 2 shows the IR spectrum of the surface of the modified PET film obtained in Example 5. -1 The presence of SCCBC on the PET surface was confirmed by the appearance of a peak around this area.

[0176] (temperature dependence) Peel tests were conducted to evaluate adhesiveness using the modified PET films of Examples 1 to 5 and the comparative PET films of Comparative Examples 1 to 4. The peel tests were conducted 7 times for Examples 1 to 3, 8 times for Examples 4 and 5, and 5 times for Comparative Examples 1 to 4, and the average peel strength was calculated for each. FIG. 3 and Table 2 show the results of the evaluation of adhesiveness in Examples 1 to 5, Comparative Example 1, and Comparative Example 2. As shown in Figure 3 and Table 2, the PET (Example 1) modified with solution (s1) (STA-TBAEMA, DEP) at 80°C had improved adhesive strength (peel strength) compared to unmodified PET (Comparative Example 1). Furthermore, as the modification temperature increased, the adhesive strength also improved significantly compared to unmodified PET. At 100°C, one of seven samples broke, at 140°C, three of eight samples, and at 160°C, seven of eight samples, demonstrating excellent adhesiveness.

[0177] (Effect of solvent) FIG. 4 and Table 2 show the results of the evaluation of adhesiveness in Example 4, Example 5, Comparative Example 3, and Comparative Example 4. As shown in Figure 4, Examples 4 and 5, which were immersed in solution (s1) (STA-TBAEMA, DEP), showed improved adhesive strength compared to the unmodified PET of Comparative Example 1. On the other hand, Comparative Examples 3 and 4, which were immersed in diethyl phthalate only, showed no improvement in adhesive strength, and the adhesive strength was equivalent to that of the unmodified PET of Comparative Example 1. This confirmed that the improvement in adhesive strength was due to SCCBC.

[0178] [Examples 3-A to 3-E, Examples 4-A to 4-D] The modified PET films of Examples 3-A to 3-E were obtained in the same manner as in Example 3, except that the immersion time was changed to the time shown in Table 3. In addition, modified PET films of Examples 4-A to 4-D were obtained in the same manner as in Example 4, except that the immersion time was changed to the time shown in Table 4.

[0179] [Table 3]

[0180] [Table 4]

[0181] (dependence of immersion time) The modified PET films of Examples 3-A to 3-E were subjected to a peel test five times to evaluate their adhesiveness. Figure 5 and Table 3 show the results of the adhesiveness evaluation for Examples 3 and 3-A to 3-E. Furthermore, a peel test was performed five times using the modified PET films of Examples 4-A to 4-D to evaluate their adhesiveness. Figure 6 and Table 4 show the results of the adhesiveness evaluation for Examples 4 and 4-A to 4-D.

[0182] As shown in Figures 5 and 6, the adhesive strength improved with increasing immersion time, and the number of samples in which the PET film itself broke during the peel test tended to increase. At 120°C, the PET film itself broke in one of five samples after 30 minutes of immersion. After one hour of immersion, the PET film itself broke in three of five samples. At 140°C, the PET film itself broke in two of five samples after 1 and 5 minutes of immersion. After 30 minutes of immersion, the PET film itself broke in four of five samples. As mentioned above, after 10 minutes of immersion at 140°C, the PET film itself broke in three of eight samples. Furthermore, the higher the modification temperature, the greater the modification effect obtained in a shorter time.

[0183] [Example 5-A to Example 5-C] The modified PET films of Examples 5-A to 5-C were obtained in the same manner as in Example 5, except that the copolymer solution was changed to the solution shown in Table 5.

[0184] [Table 5]

[0185] (Dependence of copolymer solution concentration) The modified PET films of Examples 5-A to 5-C were subjected to a peel test five times to evaluate their adhesiveness. Figure 7 and Table 5 show the results of the adhesiveness evaluation for Examples 5 and 5-A to 5-C. As shown in Figure 7, regardless of the SCCBC concentration, the adhesive strength was improved compared to unmodified PET. At an SCCBC concentration of 0.01 wt% (Example 5-A), the PET film itself broke in one of five samples, and at an SCCBC concentration of 0.5 wt% (Example 5-B) and 1.0 wt% (Example 5-C), all five of five samples.

[0186] [Example 5-a to Example 5-d] The modified PET films of Examples 5-a to 5-d were obtained in the same manner as in Example 5, except that the conditions for washing with butyl acetate after removing the PET film from the SCCBC solution were changed to the conditions shown in Table 6.

[0187] [Table 6]

[0188] (Effect of washing with butyl acetate after modification) The modified PET films of Examples 5-a to 5-d were subjected to a peel test three times to evaluate their adhesiveness. Figure 8 and Table 6 show the results of the adhesiveness evaluation for Examples 5 and 5-a to 5-d. As shown in Figure 8, no significant change in adhesive strength was observed in any of the cases. Furthermore, in Examples 5-a to 5-d, the PET film itself was destroyed in all three of the three samples. Therefore, it was found that washing with butyl acetate at room temperature had almost no effect on the adhesive strength of the modified PET film.

[0189] [Reference example 6] The PET film was immersed for 10 minutes in solution (s5) (STA-TBAEMA, xylene) heated to 120° C. The PET film was taken out of solution (s5) and air-dried for one day to obtain a modified PET film. A peel test was performed five times using the modified PET film of Reference Example 6 to evaluate adhesion, and the peel strength was 0.13 [N / mm]. Since the boiling point of xylene is about 140°C, it is difficult to heat it to above 120°C. Therefore, compared to xylene, diethyl phthalate, which can be treated at higher temperatures, is more likely to improve the modification effect.

[0190] [Example 7-A to Example 7-F] The PET film was immersed in the heated solution (s6) (STA-TBAEMA, NMP) for 10 minutes. The PET film was then removed from the solution (s6) and immersed in butyl acetate at 25°C, stirred and washed for 1 minute. The film was then dried to obtain a modified PET film. The solution temperature (modification temperature) and drying conditions in each example are as shown in Table 7. In Comparative Example 5, NMP (solvent only) was used instead of SCCBC, and treatment was carried out at the modification temperature and drying conditions shown in Table 7.

[0191] [Table 7]

[0192] The peel test was performed five times using the modified PET films of Examples 7-A to 7-F to evaluate their adhesiveness. Figure 9 and Table 7 show the results of the adhesiveness evaluation for Examples 7-A to 7-F, Comparative Examples 1 and 5. As shown in FIG. 9 and Table 7, PET modified with solution (s6) (STA-TBAEMA, NMP) had improved adhesive strength (peel strength) compared to unmodified PET (Comparative Example 1) and PET treated with NMP (solvent only) (Comparative Example 5). Breakage of the PET film itself was observed in all modified PET films (Examples 7-A to 7-F), confirming that the adhesive properties were extremely excellent. Compared to diethyl phthalate, NMP improved adhesive strength when modified at low temperatures.

[0193] [Example 8-A to Example 8-C] The PET film was immersed in the heated solution (s7) (STA-TBAEMA, DMSO) for 10 minutes. The PET film was then removed from the solution (s7) and immersed in butyl acetate at 25°C, stirred and washed for 1 minute, and then dried to obtain a modified PET film. The solution temperature (modification temperature) and drying conditions in each example are as shown in Table 8. In Comparative Example 6, DMSO (solvent only) was used instead of SCCBC, and treatment was carried out at the modification temperature and drying conditions shown in Table 8.

[0194] [Table 8]

[0195] The peel test was performed five times to evaluate the adhesiveness using the modified PET films of Examples 8-A to 8-C and the comparative PET film of Comparative Example 6. Figure 10 and Table 8 show the results of the adhesiveness evaluation for Examples 8-A to 8-C, Comparative Example 1, and Comparative Example 6. As shown in Figure 10 and Table 8, PET modified with solution (s7) (STA-TBAEMA, DMSO) had improved adhesive strength (peel strength) compared to unmodified PET (Comparative Example 1) and PET treated with DMSO (solvent only) (Comparative Example 6). Breakage of the PET film itself was observed in all modified PET films (Examples 8-A to 8-C), confirming their excellent adhesive properties. DMSO improved adhesive strength when modified at low temperatures compared to diethyl phthalate. [Industrial Applicability]

[0196] According to the present invention, the properties of the side-chain crystalline block copolymer can be utilized to impart adhesive properties and the like to polyethylene terephthalate, which is expected to lead to new applications for polyethylene terephthalate.

Claims

1. a contacting step of contacting a polyethylene terephthalate molded article with a copolymer solution containing a side-chain crystalline block copolymer and a solvent, the side-chain crystalline block copolymer comprises a first polymer block which is a repeat of a structural unit having an alkyl group having 8 or more carbon atoms in a side chain, and a second polymer block which is a repeat of a structural unit having a functional group; A method for producing a modified polyethylene terephthalate molded article, wherein the solvent contains the following (i) or (ii): (i) an ester solvent having a boiling point of 150°C or higher at 1 atm (ii) an aprotic polar solvent with a dielectric constant of 30 or more

2. the ester solvent comprises a phthalate ester compound, The method for producing a modified polyethylene terephthalate molded article according to claim 1, wherein in the contacting step, the copolymer solution and the polyethylene terephthalate molded article are contacted at 80°C or higher.

3. The method according to claim 2, wherein the phthalate ester compound is any one selected from the group consisting of dimethyl phthalate, diethyl phthalate, and dioctyl phthalate.

4. The method according to claim 2 or 3, wherein the contact is performed at a temperature of 120°C or higher and 200°C or lower.

5. the aprotic polar solvent having a dielectric constant of 30 or more includes dimethyl sulfoxide and / or N-methyl-2-pyrrolidone; The method for producing a modified polyethylene terephthalate molded article according to claim 1, wherein in the contacting step, the copolymer solution and the polyethylene terephthalate molded article are contacted at 20°C or higher and 120°C or lower.

6. The production method according to any one of claims 1 to 5, wherein the first polymer block is a polymer of any monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, each having an alkyl group having 8 or more carbon atoms.

7. The method according to any one of claims 1 to 6, wherein the second polymer block is a repeat of a structural unit having a polar group in a side chain.

8. A polyethylene terephthalate molded body and a functional layer containing a side-chain crystalline block copolymer formed on at least a part of the surface of the molded body, the side-chain crystalline block copolymer comprises a first polymer block which is a repeat of a structural unit having an alkyl group having 8 or more carbon atoms in a side chain, and a second polymer block which is a repeat of a structural unit having a functional group; The peel strength of the functional layer in a T-peel test is 0.5 N / mm or more. Modified polyethylene terephthalate molding.

9. The modified polyethylene terephthalate molded article according to claim 8, wherein the second polymer block is a repetition of a structural unit having a polar group in a side chain.

10. The modified polyethylene terephthalate molded article according to claim 8 or 9, wherein the second polymer block is a repeating structural unit having an amino group, a carboxyl group, or an oxyalkylene group in a side chain.

11. the weight average molecular weight of the first polymer block is 5,000 or more; The modified polyethylene terephthalate molded body according to any one of claims 8 to 10, wherein the weight average molecular weight of the second polymer block is 5,000 or more.

12. The modified polyethylene terephthalate molded article according to any one of claims 8 to 11, wherein a portion containing the side chain crystalline block copolymer remains on the surface even after contact with a good solvent for the side chain crystalline block copolymer.

13. A copolymer solution containing a side-chain crystalline block copolymer and a solvent, the side chain crystalline block copolymer comprises a block (A) derived from a (meth)acrylate having an alkyl group having 8 or more carbon atoms and a block (B) having a polar group in a side chain, the concentration of the side chain crystalline block copolymer is 0.01 to 2.0% by mass, The solvent comprises: Copolymer solution for modifying polyethylene terephthalate molded bodies. (i) an ester solvent having a boiling point of 150°C or higher at 1 atm (ii) an aprotic polar solvent with a dielectric constant of 30 or more

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