WO2022025124A1

WO2022025124A1 - Modified polyethylene terephthalate molded product and method for manufacturing same, and copolymer solution

Info

Publication number: WO2022025124A1
Application number: PCT/JP2021/027926
Authority: WO
Inventors: 滋八尾; 翔平井; 勇気深野
Original assignee: 学校法人福岡大学
Priority date: 2020-07-29
Filing date: 2021-07-28
Publication date: 2022-02-03
Also published as: JPWO2022025124A1

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

Modified polyethylene terephthalate molded product and its production method, and copolymer solution

The present invention relates to a modified polyethylene terephthalate molded product and a method for producing the same. The present invention also relates to a copolymer solution.

Polyethylene terephthalate (PET) is a plastic widely used for fibers, bolts, sheets, etc. because it has excellent insulation, chemical resistance, abrasion resistance, and the like. On the other hand, it is a plastic having poor adhesiveness, hydrophilicity, dyeability and the like.

Currently, as a modification method for improving the adhesiveness, hydrophilicity, dyeability, etc. of PET, methods such as plasma treatment and corona treatment are mainly used (for example, Non-Patent Document 1 and Non-Patent Document 2). Such). Due to its nature, plasma treatment and corona treatment cannot be applied to complicated shapes such as a cylinder, and the cost for introducing equipment is very high.

On the other hand, the present inventors disclose a method of modifying the surface of a fluororesin, a polyethylene resin, or a polypropylene resin by using a side chain crystalline block copolymer (SCCBC). ..

For example, Patent Document 1 describes a copolymer having a structural unit derived from the first monomer (A) and a structural unit derived from the second monomer (B), wherein the monomer (A) is the same. (Meta) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin and substituted styrene having any fluorinated alkyl group selected from the group consisting of the formulas (a1) to (a5) on the side chain. Disclosed is a method for modifying a fluororesin using a copolymer, which is any of the monomers selected from the group consisting of the above, and the monomer (B) is a monomer having a functional group.

Patent Document 2 includes a substrate whose at least a part is polyethylene and a polymer that modifies the surface of the polyethylene, and the polymer is an acrylate having an alcan chain having a length of 10 or more carbon atoms. A block copolymer of a monomer containing a monomer 1 and a second monomer which is an acrylate of a tertiary amine, or a first monomer which is a (meth) acrylate having an alcan chain having a length of 10 or more carbon atoms, and A surface modification material is disclosed which is a block copolymer of a monomer containing a second monomer which is a (meth) acrylate having a side chain having a −CF ₂ -structure having 4 or more carbon atoms.

Patent Document 3 includes a polypropylene resin molded product having a step of bringing a copolymer solution containing a side chain crystalline block copolymer and a polypropylene resin molded product into contact with each other at a temperature of the copolymer solution of 40 to 120 ° C. The modification method of the above is disclosed.

Japanese Unexamined Patent Publication No. 2016-079389 JP-A-2015-229725 Japanese Unexamined Patent Publication No. 2019-137779

As mentioned above, in order to improve the adhesiveness, hydrophilicity, dyeability, etc. of PET, it is necessary to modify PET. However, with the conventional method, there are restrictions on the shapes that can be modified, and special equipment is required. Therefore, in order to obtain a modified polyethylene terephthalate molded product having good adhesiveness and the like, there has been a demand for a method for easily modifying the PET surface.

Further, in the methods disclosed in Patent Documents 1 to 3, the resin to be modified is a vinyl-based resin, and the object is to utilize SCBCBC having a structure relatively similar to the resin to be modified in the side chain. The resin of is modified.
However, the SCCBC disclosed in Patent Documents 1 to 3 does not have much similarities to the condensation-based resin such as the PET resin to be modified in the present invention. So far, modifications using SCCBC have not been sufficiently investigated for resins that do not have much similarities to SCCBC.

An object of the present invention is to provide a modified polyethylene terephthalate molded product having excellent surface properties and a method for producing the same.

As a result of diligent research to solve the above problems, the present inventor has found that the following invention meets the above object, and has reached the present invention.

That is, the present invention relates to the following invention.
<1> It has a contact step of bringing a copolymer solution containing a side chain crystalline block copolymer and a solvent into contact with a polyethylene terephthalate molded product.
The side chain crystalline block copolymer is a first polymerization block in which a structural unit having an alkyl group having 8 or more carbon atoms in the side chain is repeated, and a second polymer in which the structural unit has a functional group is repeated. Including polymerization blocks
A method for producing a modified polyethylene terephthalate molded product, wherein the solvent comprises the following (i) or (ii).
(I) Ester-based solvent having a boiling point of 150 ° C. or higher at 1 atm (ii) Aprotonic polar solvent having a dielectric constant of 30 or higher <2> The ester solvent contains a phthalate ester compound and contains.
The method for producing a modified polyethylene terephthalate molded product according to <1>, wherein in the contact step, the copolymer solution and the polyethylene terephthalate molded product are brought into contact with each other at 80 ° C. or higher.
<3> The production method according to <2>, wherein the phthalate ester compound is selected from the group consisting of dimethyl phthalate, diethyl phthalate, and dioctyl phthalate.
<4> The production method according to <2> or <3>, wherein the contact is at 120 ° C. or higher and 200 ° C. or lower.
<5> The aprotic polar solvent having a dielectric constant of 30 or more contains dimethyl sulfoxide and / or N-methyl-2-pyrrolidone.
The method for producing a modified polyethylene terephthalate molded product according to <1>, wherein in the contact step, the copolymer solution and the polyethylene terephthalate molded product are brought into contact with each other at 20 ° C. or higher and 120 ° C. or lower.
<6> The first polymerization block is selected from the group consisting of (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin and substituted styrene having an alkyl group having 8 or more carbon atoms. The production method according to any one of <1> to <5>, which is a polymer of any of the monomers.
<7> The production method according to any one of <1> to <6>, wherein the second polymerization block is a repetition of a structural unit having a polar group in a side chain.
<8> A polyethylene terephthalate molded product and a functional layer containing a side chain crystalline block copolymer formed on at least a part of the surface of the molded product are provided.
The side chain crystalline block copolymer is a first polymerization block in which a structural unit having an alkyl group having 8 or more carbon atoms in the side chain is repeated, and a second polymer in which the structural unit has a functional group is repeated. Including polymerization blocks
A modified polyethylene terephthalate molded product having a peel strength of 0.5 N / mm or more in the T-type peel test of the functional layer.
<9> The modified polyethylene terephthalate molded product according to <8>, wherein the second polymerization block is a repetition of a structural unit having a polar group in the side chain.
<10> The modified polyethylene terephthalate according to any one of <8> or <9>, wherein the second polymerization block is a repetition of a structural unit having an amino group, a carboxyl group or an oxyalkylene group in the side chain. Molded body.
<11> The weight average molecular weight of the first polymerization block is 5,000 or more.
The modified polyethylene terephthalate molded product according to any one of <8> to <10>, wherein the weight average molecular weight of the second polymerization block is 5,000 or more.
<12> Any of the above <8> to <11>, wherein the portion containing the side chain crystalline block copolymer remains on the surface even after contacting with a good solvent of the side chain crystalline block copolymer. The modified polyethylene terephthalate polymer described in Crab.
<13> A copolymer solution containing a side chain crystalline block copolymer and a solvent.
The side chain crystalline block copolymer includes 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 in which the solvent comprises the following (i) or (ii).
(I) Ester-based solvent having a boiling point of 150 ° C. or higher at 1 atm (ii) Aprotic polar solvent having a dielectric constant of 30 or higher.

According to the present invention, a modified polyethylene terephthalate molded product having excellent surface characteristics and a method for producing the same are provided. For example, according to the present invention, there is provided a modified polyethylene terephthalate molded product having good adhesiveness and a method for producing the same.

It is a figure for demonstrating the test piece used for the peeling test of the Example of this invention, and the calculation method of data. It is a figure which shows the FT-IR analysis result of the modified PET film which concerns on Example of this invention. It is a figure which shows the evaluation result of the adhesiveness of the modified PET film modified by the copolymer solution (STA-TBAEMA, DEP) at different modification temperatures. It is a figure which shows the evaluation result of the adhesiveness of the modified PET film modified using only diethyl phthalate or a copolymer solution (STA-TBAEMA, DEP). It is a figure which shows the evaluation result of the adhesiveness of the modified PET film modified by the copolymer solution (STA-TBAEMA, DEP) at different immersion times. It is a figure which shows the evaluation result of the adhesiveness of the modified PET film modified by the copolymer solution (STA-TBAEMA, DEP) at different immersion times. It is a figure which shows the evaluation result of the adhesiveness of the modified PET film modified by using the copolymer solution (STA-TBAEMA, DEP) with different SCCBC concentrations. It is a figure which shows the evaluation result of the adhesiveness of the modified PET film modified under the washing conditions of a copolymer solution (STA-TBAEMA, DEP) and different butyl acetate. It is a figure which shows the evaluation result of the adhesiveness of the modified PET film modified by the copolymer solution (STA-TBAEMA, NMP) at different modification temperatures. It is a figure which shows the evaluation result of the adhesiveness of the modified PET film modified by the copolymer solution (STA-TBAEMA, DMSO) at different modification temperatures.

Hereinafter, embodiments of the present invention will be described in detail, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is described below unless the gist thereof is changed. It is not limited to the contents of. In addition, when the expression "-" is used in this specification, it shall be used as an expression including numerical values or physical property values before and after the expression.

<Manufacturing method of modified polyethylene terephthalate molded product>
The present invention has a contact step of bringing a copolymer solution containing a side chain crystalline block copolymer and a solvent into contact with a polyethylene terephthalate molded product, and the side chain crystalline block copolymer is formed on the side chain. Production of a modified polyethylene terephthalate molded product comprising a first polymerization block which is a repetition of a structural unit having an alkyl group having 8 or more carbon atoms and a second polymerization block which is a repetition of a structural unit having a functional group. It relates to a method (hereinafter, may be referred to as "a method for producing a modified PET of the present invention").

The present inventors make a PET molded product by contacting a copolymer solution containing the side chain crystalline block copolymer (hereinafter, simply referred to as “block copolymer”) and a solvent with the PET molded product. It was found that it can be reformed. By contacting the copolymer solution, the PET surface becomes loose and swells, and the alkyl group having 8 or more carbon atoms in the side chain of the first polymerization block can penetrate into the PET molded product. It is considered that the block copolymer adheres to the block copolymer and the functionality of the block copolymer can be imparted to the PET molded product.

[First polymerization block]
The first polymerization block (hereinafter referred to as “block (A)”) is a repeating structural unit having an alkyl group having 8 or more carbon atoms in the side chain. In the block (A), an alkyl group having a length of 8 or more carbon atoms in the side chain is directly bonded to the main chain portion of the block (A), or a linking group (ester bond, amide bond, ether bond, benzene). They are connected via a ring, etc.). This block (A) becomes a portion showing side chain crystallinity due to the alkyl group of the side chain. It is presumed that this side chain crystalline site interacts with the PET molded product. The adhesiveness between the block copolymer and the PET molded product can be adjusted according to the number of carbon atoms and the structure of the side chain of the block (A).

The alkyl group having 8 or more carbon atoms in the side chain of the block (A) preferably has 10 or more carbon atoms, more preferably 12 or more, and even more preferably 14 or more. Further, the alkyl group is preferably a linear alkyl group. On the other hand, the upper limit thereof can be appropriately set as long as it can be polymerized as a copolymer and the adhesiveness with the PET molded product can be maintained. As a specific upper limit, in reality, the number of carbon atoms is preferably 50 or less, more preferably 40 or less. Further, the number of carbon atoms may be 30 or less or 25 or less. If the number of carbon atoms of the alkyl group is too large, it may not be possible to obtain an appropriate three-dimensional structure as a copolymer, or it may be difficult to set the polymerization conditions.

Specific examples of the alkyl group having 8 or more carbon atoms include a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group (stearyl group), a docosyl group (behenyl group) and the like.

The degree of polymerization of the block (A) is 2 or more. The degree of polymerization of the block (A) may be appropriately selected depending on the structure of the block copolymer and the like within a range in which the adhesiveness with the PET molded product can be maintained. In order to improve the adhesiveness with the PET molded product, the degree of polymerization of the block (A) is preferably 7 or more, and may be 8 or more or 10 or more. The degree of polymerization of the 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.

The molecular weight corresponding to the block (A) is preferably 3,000 or more. When the molecular weight corresponding to the block (A) is 3,000 or more, it can be more firmly adhered to the PET molded product. The molecular weight corresponding to the block (A) may be 4,000 or more or 5,000 or more. Further, it may be 20,000 or less, 15,000 or less, 10,000 or less, or 8,000 or less.

Note that these molecular weights are values "Mw: weight average molecular weight" that can be obtained in terms of polystyrene from the results obtained by GPC. In addition, the reforming copolymer may be difficult to dissolve in a solvent and it may be difficult to measure the molecular weight. In such a case, each molecular weight can be calculated by a method such as elemental analysis, IR, or NMR.

The first polymerization block (block (A)) is composed of (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin and substituted styrene having an alkyl group having 8 or more carbon atoms in the side chain. It is preferably a polymer of any of the monomers selected from the group (hereinafter referred to as “monomer (a)”). That is, it is preferable that the block copolymer contains the structural unit (A) derived from the monomer (a).

As the monomer (a), a commercially available one or an appropriately synthesized one can be used.

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.

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

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

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

As the α-olefin having an alkyl group having 8 or more carbon atoms, an α-olefin obtained by decarbonylation of an aliphatic carboxylic acid having 11 or more carbon atoms can be used.

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

Here, in the present application, "(meth) acrylate" means both acrylate and methacrylate. Similarly, "(meth) acrylamide" means both acrylamide and metaacrylamide.

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), and docosyl methacrylate. (Behenyl methacrylate) and the like.

In addition, 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, palmitic acid. Examples thereof include vinyl, vinyl stearate, 1-tridecene, 1-pentadecene, 4-n-octylstyrene and the like.

The monomer (a) is preferably a (meth) acrylate or α-olefin monomer having an alkyl group having 8 or more carbon atoms in the side chain, and an alkyl having 8 or more carbon atoms in the side chain. More preferably, it is a (meth) acrylate having a group.

The block (A) has 8 or more carbon atoms from the viewpoints of easy availability of the monomer (a), easy control of polymerization conditions, and easy interaction between alkyl groups having 8 or more carbon atoms. A (meth) acrylate having an alkyl group having a length of 8 or more, or a polymer of an α-olefin having an alkyl group having a length of 8 or more carbon atoms is preferable.

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

In the general formulas (A-1) and (A-2), ^Ra1 represents a hydrogen atom or a methyl group.

In the general formulas (A-1) and (A-2), ^Ra2 represents an alkyl group having 8 or more carbon atoms. As described above, R ^a2 is preferably a linear alkyl group. The number of carbon atoms of the alkyl group represented by ^Ra2 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, 25 or less, and the like.

In the general formulas (A-1) and (A-2), m is an integer of 2 or more. The m is preferably 7 or more, preferably 8 or more, or 10 or more. Further, 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.

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

Here, the functional group imparts functionality to the PET molded product by being present in large numbers in the block copolymer even after the copolymerization. The functionality imparted to the PET molded body mainly includes adhesiveness, hydrophilicity, dyeability, ion conductivity, metal adsorption ability, metal supporting property, plating adhesion and the like. The functional group possessed by the block (B) means a group capable of imparting these functionalities. The functional group is appropriately selected in consideration of the function to be imparted and the ease of polymerization of the copolymer, and may have two or more functional groups in the constituent unit of the block (B).

Since the functionality derived from the functional group is likely to be exhibited on the surface of the PET molded product and the modification effect is large, it is preferable to have the functional group in the side chain portion of the block (B). At this time, the functional group (particularly, the polar group) of the side chain is directly bonded to the main chain portion of the block (B), or has a linking group (ester bond, amide bond, ether bond, benzene ring, etc.). They are connected through. In this case, the structure of the main chain is not particularly limited because the portion of the block (B) that becomes the main chain has little effect on the modification.

The degree of polymerization of the block (B) is an integer of 2 or more. The degree of polymerization of the block (B) is appropriately determined according to the structure of the block copolymer. The degree of polymerization of the block (B) is preferably 2 to 1,000. In order to exert a more stable reforming effect, it is more preferably 5 or more or 10 or more. Further, it may be 20 or more, 30 or more, and 40 or more. The degree of polymerization of the block (B) may be 800 or less, 500 or less, 300 or less, 100 or less, or 60 or less.

The molecular weight corresponding to the block (B) is preferably 500 or more. When the molecular weight corresponding to the block (B) is 500 or more, a copolymer having further excellent adhesiveness to other materials can be obtained. The molecular weight corresponding to the block (B) is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. Further, it may be 20,000 or less, 15,000 or less, or 12,000 or less.

The functional group of the block (B) is preferably a polar group. The polar group refers to a group of polar atomic groups that, when present in a polymer using a monomer having the group, form a structure showing polarity in the polymer.
Having a polar group is excellent in that the characteristics of the obtained modified PET molded product are significantly different from those of a normal PET molded product (PET molded product before modification). In particular, when the block (B) contains a polar group, a modified PET molded product having excellent adhesiveness to other materials can be obtained.

Typical polar groups include an amino group, an ammonium group, a carboxyl group, a hydroxyl group, a sulfonic acid group, an alkoxy group, an oxylanyl group, an oxyalkylene group, a carbonyl group, an ether group, a sulfonyl group, an ester group and an amide group. Be done.

The 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. Further, the block (B) is preferably a repeating structural unit having an oxyalkylene group in the side chain. Further, the block (B) is preferably a repeating structural unit having a carboxyl group in the side chain.

For example, block (B) is any monomer selected from the group consisting of (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin and substituted styrene having a polar group in the side chain. It can be a polymer (hereinafter referred to as "monomer (b)"). That is, the block copolymer can include the structural unit (B) derived from the monomer (b). Further, the block (B) may be a (meth) acrylic acid polymer.

As the monomer (b), a commercially available one or an appropriately synthesized one can be used.

The block (B) can be a polymer of a monomer having an amino group. At this time, the monomer (b) is a monomer having an amino group, and a monomer having an amino group in its side chain is preferable.

Here, the amino group may be unsubstituted or has a substituent. Examples of the substituent of 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 is a general formula "-NR ^x1 R ^x2 (where R ^x1 and R ^x2 are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or carboxyalkyl groups having 1 to 4 carbon atoms). It is preferable that it is a group represented by. Examples of such amino groups include -NH ₂ , -N (CH ₃ ) ₂ , -N (C ₂ H ₅ ) ₂ , -NH (tert-C ₄ H ₉ ), and -N (CH ₂ COOH) ₂ . Can be mentioned.

Further, the block (B) can be a polymer of a monomer having an oxyalkylene group. At this time, the monomer (b) can be a monomer having an oxyalkylene group, and a monomer having an oxyalkylene group in its side chain is preferable.

The oxyalkylene group is a divalent group represented by "-(C _p H _2p -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).

-(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, and R ^y1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

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.

Specific examples of the monomer (b) are 2- (Dimethylamino) ethyl Methacrylate, DMAEMA, 2- (Dimethylamino) ethyl Acrylate, DMAEA. , 2- (Diethylamino) ethyl methacrylate (2- (Diethylamino) ethyl Methacrylate, DEAEMA), 2- (diethylamino) ethyl acrylate (2- (Diethylamino) ethyl Acrylate, DEAEA), 2- (tert-butylamino) ethyl methacrylate ( 2- (tert-Butylamino) ethyl Methacrylate, TBAEMA), N, N-dimethylacrylamide (N, N-Dimethylacrylamide, DMAA), N, N-dimethylaminopropylacrylamide (N, N-Dimethylaminopropyl Acrylamide, DMAPAA), and N , N-diethylacrylamide, DEAA and other monomers having an amino group.

In addition, N- [3- (dimethylamino) propyl] acrylamide, N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (diethylamino) ethyl] acrylamide, 2- (vinyloxy) ethaneamine, 3-amino. -1-Propen (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] Examples thereof include monomers having an amino group such as styrene and N, N-dimethylvinylbenzylamine.

Further, as the monomer (b), methoxy-polyethylene glycol-acrylate (CH ₂ = CH (CO) O (CH ₂ -CH ₂ -O-) _q CH ₃ ) (q = 2 to 10), ethoxy-polyethylene glycol- Acrylate (CH ₂ = CH (CO) O (CH ₂ -CH ₂ -O-) _q C ₂ H ₅ ) (p = 2, q = 2-10), polyethylene glycol-monoacrylate (CH ₂ = CH (CO) ) O (CH ₂ -CH ₂ -O-) _q H) (q = 2 to 10) and the like, examples thereof include monomers having an oxyalkylene group. More specifically, di (ethylene glycol) ethyl ether acrylate (CH ₂ = CH (CO) O (CH ₂ -CH ₂ -O-) ₂ C ₂ H ₅ , Diethylen Glycol Monoethyl Ether Acrylate, DEEA) and deca Examples thereof include monomers having an oxyalkylene group such as (ethylene glycol) ethyl ether acrylate (CH ₂ = CH (CO) O (CH ₂ -CH ₂ -O-) ₁₀ C ₂ H ₅ ).

Examples thereof include monomers having an oxyalkylene group such as ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, and tetraethylene glycol methyl vinyl ether.

Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, 2- (methacryloyloxy) ethanesulfonic acid, ATBS (Acrylamide Tertiary Butyl Sulfonic Acid), and ATBSNa which is a sodium salt thereof. Examples of the monomer having a hydroxyl group or a carboxy group include acrylic acid, a sodium salt thereof, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate.
Further, the block (B) may have a structure in which a polymer of a monomer having a reactive group such as an oxylanyl group in the side chain (hereinafter referred to as “monomer (b1)”) reacts with an amine. can.

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

The block (B) can have, for example, the structures of the following general formulas (B-1) to (B-4).

In the general formulas (B-1) to (B-4), R ^b1 represents a hydrogen atom or a methyl group.

In the general formulas (B-1) to (B-4), ^RL represents a single bond or an alkylene group, and is preferably a single bond or an alkylene group having 1 to 4 carbon atoms.

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

In the general formulas (B-1) to (B-4), R ^b2 is 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 oxylanyl group and the above general formula ( Represents any one selected from the group consisting of groups represented by 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), preferably a hydrogen atom and an amino. It is more preferable that the group is selected from the group consisting of a group and a group represented by the above general formula (Y).
The preferred amino group and the mode of the group represented by the general formula (Y) are as described above.

In the general formula (B-2), R ^b3 represents a hydrogen atom or an alkyl group, and a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferable.

In the 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. Further, 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.

The block (B) represented by the general formula (B-1) can be, for example, a polymerized aminoalkyl (meth) acrylate. As the aminoalkyl (meth) acrylate, a commercially available one or one obtained by reacting (meth) acrylate with an alkanolamine can be used.

Further, the block (B) represented by the general formula (B-1) can be, for example, a polymer of a polyalkylene glycol mono (meth) acrylate or an alkoxypolyalkylene glycol mono (meth) acrylate. Polyalkylene glycol mono (meth) acrylates and alkoxypolyalkylene glycol mono (meth) acrylates are commercially available or obtained by reacting (meth) acrylate with polyalkylene glycol or polyalkylene glycol monoalkyl ether. Etc. can be used.

The block (B) represented by the general formula (B-2) can be, for example, a polymer of alkyl (meth) acrylamide or aminoalkyl (meth) acrylamide. As the alkyl (meth) acrylamide, commercially available ones, those obtained by reacting (meth) acrylate with an alkylamine, and the like can be used. As the aminoalkyl (meth) acrylamide, commercially available ones, those obtained by reacting (meth) acrylate with alkylenediamine, and the like can be used.

The block (B) represented by the general formula (B-3) can be, for example, a polymer of aminoalkyl vinyl ether. As the aminoalkyl vinyl ether, commercially available ones, those obtained by reacting methyl vinyl ether with alkanolamine, and the like can be used.

Further, the block (B) represented by the general formula (B-3) can be, for example, a polymer of polyalkylene glycol monovinyl ether or alkoxypolyalkylene glycol monovinyl ether. As the polyalkylene glycol monovinyl ether and the alkoxypolyalkylene glycol monovinyl ether, commercially available ones, those obtained by reacting methyl vinyl ether with polyalkylene glycol or polyalkylene glycol monoalkyl ether, and the like can be used.

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

Further, the block (B) can have the structures of the following general formulas (B-5) to (B-7).

In the general formulas (B-5) to (B-7), R ^b4 represents a hydrogen atom or a methyl group.

In the general formulas (B-5) to (B-7), ^RL represents a single bond or an alkylene group, and is preferably a single bond or an alkylene group having 1 to 4 carbon atoms.

In the general formulas (B-5) to (B-7), R ^b5 is represented by an amino group, an ammonium group, a carboxyl group, a hydroxyl group, a sulfonic acid group, an alkoxy group, an oxylanyl group, and a general formula (Y). Represents one selected from the group consisting of groups.
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 amino group and the mode of the group represented by the general formula (Y) are as described above.

In the general formulas (B-5) to (B-7), n is an integer of 2 or more. n may be 5 or more, 10 or more, 20 or more, 30 or more, and 40 or more. Further, 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.

The block (B) represented by the general formula (B-6) can be, for example, a polymerized allylamine. As the allylamine, a commercially available product or a product obtained by reacting allyl alcohol with ammonia or an alkylamine can be used.

Further, the block (B) represented by the general formula (B-6) can be, for example, a polymer of polyalkylene glycol monoallyl ether or alkoxypolyalkylene glycol monoallyl ether. As the polyalkylene glycol monoallyl ether and the alkoxypolyalkylene glycol monoallyl ether, commercially available ones or those obtained by reacting allyl halide with polyalkylene glycol or polyalkylene glycol monoalkyl ether can be used. can.

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

The block (B) represented by the general formula (B-7) can be, for example, a polymer of polyalkylene glycol monovinylbenzyl ether or alkoxypolyalkylene glycol monovinylbenzyl ether. As the polyalkylene glycol monovinylbenzyl ether and the alkoxypolyalkylene glycol monovinylbenzyl ether, commercially available ones, those obtained by reacting a vinylbenzyl halide with polyalkylene glycol or polyalkylene glycol monoalkyl ether, and the like can be used. can.

The block (B) is preferably a general formula (B-1) or a general formula (B-2), and is preferably a general formula, from the viewpoint of easy availability of a monomer as a raw material and easy control of polymerization conditions. (B-1) is more preferable.

[Side chain crystalline block copolymer]
The side chain crystalline block copolymer has a first polymerization block (block (A)) having an alkyl group having 8 or more carbon atoms in the side chain and a second polymerization block (block (B)) having a functional group. ) And.
By forming a block copolymer, it becomes easy for each function to be fully exhibited.
This block copolymer may be composed of a block (A) and a 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 substantially of the block (A) and the block (B), and in the side-chain crystalline block copolymer, the block (A) and the block (A) and the block (B). The total content of B) can be 95% by mass or more, 98% by mass or more, and the like. Further, the block copolymer may be any of a diblock copolymer, a triblock copolymer and the like.

The side chain crystalline block copolymer preferably has a block (A) having a molecular weight of 3,000 or more and a block (B) having a molecular weight of 500 or more. By having such a molecular weight, the PET molded product and the block copolymer can be stably adhered to each other. It is more preferable that the block (A) has a molecular weight of 5,000 or more, the block (B) has a molecular weight of 1,000 or more, and the block (A) has a molecular weight of 5,000 or more. It is more preferable that the molecular weight of the block (B) is 5,000 or more.

The side chain crystalline block copolymer is more preferably the following (p1) to (p3).
(P1) A block copolymer (p2) 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. A block 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 a group represented by the above general formula (Y). Block copolymer (p3) 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 (meth) acrylic acid.

One of the preferred block copolymers is a block copolymer containing the block (A) represented by the general formula (A-1) and the block (B) represented by the general formula (B-1). Is. By using such a block copolymer, the block (A) and the PET molded product are firmly adhered to each other, and the function of the block (B) can be easily expressed.

More specifically, as the block copolymer, for example, the following can be used.

The polymerization method of the block copolymer is not particularly limited, and it is possible to polymerize by a known technique such as various living polymerization methods (radicals, anions, cations). As the living radical polymerization method, an NMP method, an ATRP method, a RAFT method and the like can be used.

For example, the monomer (a) is mixed with the polymerization solvent together with the initiator to prepare the monomer (a) mixed solution, and the monomer (a) mixed solution preparation step is performed. Next, the monomer (a) mixed solution prepared in this mixed solution preparation step is appropriately stirred in a reactor at an appropriate polymerization temperature (for example, about 90 to 120 ° C.), and a living radical is subjected to a nitrogen atmosphere or the like. The monomer (a) polymerization step based on the polymerization mechanism of the initiator such as polymerization is carried out to obtain the monomer (a) polymer. Further, a monomer (b) polymerization step is performed in which the monomer (b) is mixed with the solution in which the monomer (a) polymer is mixed, and the monomer (b) is further polymerized by a radical or the like in the solution. Thereby, a block copolymer containing the block (A) derived from the monomer (a) and the block (B) derived from the monomer (b) can be obtained. The order in which the monomer (a) and the monomer (b) are polymerized can also be changed according to the type of the monomer to be polymerized, the molecular weight, the polymerization conditions of each, and the like.

When other monomers are contained, they may be added to the monomers (a) and the monomers (b) and polymerized as the third monomer.

Further, a monomer (a) and a monomer (b1) having a reactive group such as an oxylanyl group on its side chain are polymerized to synthesize a precursor polymer, and then reacted with an amine or the like to form a block copolymer. You may get it.

Specifically, in the same manner as described above, the monomer (a) is mixed with the polymerization solvent together with the initiator, and at an appropriate polymerization temperature (for example, about 90 to 120 ° C.), the nitrogen atmosphere and the like are appropriately stirred in the reactor. Under the above, a monomer (a) polymerization step based on the polymerization mechanism of the initiator such as living radical polymerization is carried out to obtain a monomer (a) block polymer. In the solution in which the monomer (a) block polymer is mixed, the monomer (b1) (for example, (meth) acrylate, (meth) acrylamide having an oxylanyl group, vinyl ether, vinyl ester, siloxane, α-olefin and substitution is added. Any monomer selected from the group consisting of styrene) is mixed, and a monomer (b1) polymerization step is performed in which the monomer (b1) is further polymerized by a radical or the like in the solution. As a result, a solution in which the precursor polymer having the block (A) derived from the monomer (a) and the block (B1) derived from the monomer (b1) is mixed is obtained. Next, when iminodiacetic acid is reacted with this precursor polymer, the oxylanyl group reacts with iminodiacetic acid and has an amine structure derived from iminodiacetic acid (a structure having an amino group substituted with a carboxyalkyl group in the side chain). ) A block copolymer (for example, the above-mentioned (IX) copolymer) is obtained.

[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 to an arbitrary value, and it becomes easy to impart desired functionality such as adhesiveness to a desired range of the PET molded product.

In the present application, the block copolymer solution is a concept that includes not only a uniform solution in which the block copolymer is completely dissolved in a solvent, but also a suspension / dispersion solution. Depending on the structure of the block copolymer, it may be difficult to completely dissolve the block copolymer in the solvent. Therefore, the block copolymer can be used as a suspension or a dispersion liquid in which the block copolymer is dispersed or suspended in the solvent. good.

(solvent)
Examples of the solvent for the copolymer solution include ester solvents such as butyl acetate, octyl acetate, methyl benzoate, ethyl benzoate, octyl benzoate, dimethyl phthalate, diethyl phthalate, and dioctyl phthalate; N-methyl-2- Amid solvents such as pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide; ether solvents such as tetrahydrofuran, dimethoxyethane, cyclopentylmethyl ether, diethylene glycol methyl ether, anisole, methylanisole; methylisobutylketone, cyclohexanone, Examples thereof include a ketone solvent such as acetophenone; a sulfoxide solvent such as dimethyl sulfoxide; a nitrile solvent such as acetonitrile; and an aprotonic polar solvent such as a phosphate amide solvent such as hexamethylphosphate triamide.

Examples of the solvent for the copolymer solution include protonic solvents such as ethanol, isopropyl alcohol, butanol, ethylene glycol, glycerin, 2-methoxyethanol and 2-ethoxyethanol.

Further, as the solvent of the copolymer solution, an aromatic hydrocarbon solvent such as toluene, xylene (o-xylene, m-xylene, p-xylene, and a mixture thereof), mecitylene, ethylbenzene, cyclohexylbenzene, etc.; Halogenized aromatic hydrocarbon compounds such as chlorobenzene, dichlorobenzene, trichlorobenzene, bromobenzene and fluorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, cyclohexane and decalin; trichloromethane, tetrachloromethane, Halogenated aliphatic hydrocarbon solvents such as dichloroethane, trichloroethylene, tetrachloroethylene, chlorobutane and tribromomethane; non-polar solvents such as ether solvents such as dioxane and diethyl ether can be mentioned.

As the solvent, only one kind or two or more kinds of solvents can be appropriately mixed and used.

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

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

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 used as a mixed solvent, these solvents are preferably the main solvent, and the total volume of the solvents preferably occupies 50% by volume or more of the ester solvent or the aprotic polar solvent having a dielectric constant of 30 or more. It may occupy 70% by volume or more, 80% by volume or more, 90% by volume or more, and 95% by volume or more.

Even if the ester-based solvent is an aliphatic ester compound (butyl acetate, octyl acetate, etc.), an aromatic ester compound (methyl benzoate, ethyl benzoate, octyl benzoate, etc., benzoate ester, dimethyl phthalate, phthalate, etc.) It may be a phthalate ester compound such as diethyl acid or dioctyl phthalate), but an aromatic ester compound is preferable, and a phthalate ester compound is more preferable.

Further, as will be described later, when an ester solvent is used, a higher modification effect can be obtained by heating the PET molded product at the time of contact. Therefore, the ester solvent has a boiling point of 80 ° C. or higher at 1 atm. Is preferable, and more preferably 100 ° C. or higher, 120 ° C. or higher, 150 ° C. or higher, 200 ° C. or higher, and 220 ° C. in that order. When the boiling point of the ester solvent is lower than the temperature at the time of contact between the copolymer solution and the PET molded product, reflux may be performed in order to suppress changes in the liquid volume and concentration of the copolymer solution due to volatilization. If a solvent having a low boiling point is used, it may be difficult to bring the copolymer solution and the PET molded product into contact with each other at a target temperature, or it may be necessary to improve the reflux function and the operability may be deteriorated. Therefore, the boiling point of the ester solvent is preferably in the above range. On the other hand, it is not necessary to set an upper limit of the boiling point.

Examples of the aprotic polar solvent having a dielectric constant of 30 or more (hereinafter, the numbers in parentheses indicate the dielectric constant) include N-methyl-2-pyrrolidone (32), N, N-dimethylacetamide (38), and N. , N-dimethylformamide (38) and other amide solvents; dimethylsulfoxide (47) and other sulfoxide solvents; acetonitrile (37) and other nitrile solvents; hexamethylphosphate triamide (31) and other phosphate amide solvents. And so on.
Of these, sulfoxide-based solvents and / or amide-based solvents are preferable, and dimethyl sulfoxide and / or N-methyl-2-pyrrolidone are more preferable.

(concentration)
The concentration of the block copolymer in the copolymer solution can be appropriately set according to the type and modification temperature of the block copolymer, the adhesion amount and adhesion film thickness of the copolymer, the purpose of modification, and the like. The concentration of the block copolymer in the copolymer solution is preferably 0.01 to 2.0% by mass. The lower limit of the concentration of the block copolymer is preferably 0.02% by mass or more, more preferably 0.05% by mass or more. If the concentration of the block copolymer is too low, the modifying effect on the PET molded product may be insufficient. The upper limit of the concentration of the block copolymer is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. It may be 0.8% by mass or less, 0.6% by mass or less, or 0.5% by mass or less. Even if the concentration of the block copolymer is increased, the modifying effect on the PET molded product may be saturated. Further, if the concentration of the block copolymer is too high, micelle formation due to self-assembly of the block copolymer itself may occur, and the modification effect may not be sufficiently exhibited.

A (meth) acrylate containing a side chain crystalline block copolymer and a solvent as a copolymer solution for modifying polyethylene terephthalate, and the side chain crystalline block copolymer has an alkyl group having 8 or more carbon atoms. The block (A) derived from the above and the block (B) having a polar group in the side chain are contained, and the concentration of the side chain crystalline block copolymer is 0.01 to 2.0% by mass, and the solvent is used. However, a solution containing the following (i) or (ii) can be mentioned.
(I) Ester-based solvent having a boiling point of 150 ° C. or higher at 1 atm (ii) Aprotic polar solvent having a dielectric constant of 30 or higher.

For example, the copolymer solution for modifying polyethylene terephthalate includes 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. A solution containing a block copolymer and a solvent, the solvent containing an ester solvent having a boiling point of 150 ° C. or higher at 1 atm, and a block copolymer concentration of 0.01 to 2.0% by mass (hereinafter, "co-polymer"). It may be described as "polymer solution (L1)").

By using the copolymer solution (L1), the polyethylene terephthalate molded product and the block copolymer can be adhered more firmly.

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

In the block copolymer solution (L1), the block copolymer is represented by a block (A) derived from a (meth) acrylate having an alkyl group having 8 or more carbon atoms, an amino group, and the above general formula (Y). It is preferably a block copolymer containing a block (B) having a group or a carboxyl group in the side chain. Further, the block copolymer is a block (A) derived from a (meth) acrylate having an alkyl group having 8 or more carbon atoms, a (meth) acrylate having an amino group, and a group represented by the above general formula (Y). It is more preferable that it is a block copolymer containing a (meth) acrylate having a (meth) acrylate or a block (B) derived from (meth) acrylic acid.

Further, the copolymer solution for modifying polyethylene terephthalate includes 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. A solution containing a block copolymer and a solvent, wherein the solvent contains an aprotonic polar solvent having a dielectric constant of 30 or more, and the concentration of the block polymer is 0.01 to 2.0% by mass (hereinafter, "" It may be described as "copolymer solution (L2)").

By using the copolymer solution (L2), the polyethylene terephthalate molded product and the block copolymer can be adhered more firmly.

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

In the block copolymer solution (L2), the block copolymer is represented by a block (A) derived from a (meth) acrylate having an alkyl group having 8 or more carbon atoms, an amino group, and the above general formula (Y). It is preferably a block copolymer containing a block (B) having a group or a carboxyl group in the side chain. Further, the block copolymer is a block (A) derived from a (meth) acrylate having an alkyl group having 8 or more carbon atoms, a (meth) acrylate having an amino group, and a group represented by the above general formula (Y). It is more preferable that it is a block copolymer containing a (meth) acrylate having a (meth) acrylate or a block (B) derived from (meth) acrylic acid.

[Polyethylene terephthalate (PET) molded product]
The polyethylene terephthalate (PET) molded product is a molded product containing polyethylene terephthalate as a main component (for example, containing 50% by mass or more), and includes polyethylene terephthalate, a copolymer thereof, a mixture of polyethylene terephthalate and another resin, and the like. It is molded into an arbitrary shape. This molded product may appropriately contain a functionalizing agent such as a molding aid, a pigment, and an ultraviolet absorber.

Further, the molding form of the PET molded body is not particularly limited, and examples thereof include molded bodies such as films, plates, particles, fibers, and porous materials. In the method for producing a modified PET molded product of the present invention, even if the base material to be modified is a porous material, not only the surface corresponding to the surface layer of the molded product but also the inside of the PET molded product such as inside the pores. The copolymer solution can be infiltrated to modify the entire porous material.

[Contact process]
The method for producing a modified PET molded product of the present invention includes a step of bringing a polyethylene terephthalate molded product into contact with a copolymer solution containing a side chain crystalline block copolymer and a solvent.

The contact method between the copolymer solution and the PET molded body is not particularly limited as long as it can form a functional layer containing the block copolymer in the portion of the PET molded body to be modified. Depending on the shape of the PET molded body, the range to be modified, etc., a method capable of contacting the copolymer solution with the portion of the PET molded body to be modified may be appropriately selected, and the contact method may be used. Examples include dip coating, spin coating, applicator coating, slit coating, die coating, bar coating, screen printing, inkjet printing, gravure printing, spray coating, and pouring. Since the copolymer solution can be easily controlled at a predetermined temperature, one of the preferred contact methods is a method of immersing the PET molded product in the copolymer solution.

The temperature (modification temperature) at which the block copolymer and the PET molded product are brought into contact with each other can be appropriately determined according to the type of solvent in the copolymer solution, the shape of the PET molded product, the contact time, and the like.

When the solvent of the copolymer solution contains an ester solvent, the reforming temperature is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, 120 ° C. or higher, and 130 ° C. or higher in that order. The ester solvent has a dielectric constant of about 5 to 10, and the surface of the PET molded product is not easily eroded at about room temperature, and the modification may take a long time or the modification effect may be insufficient. By setting the reforming temperature to 80 ° C. or higher, loosening and swelling of the surface of the PET molded product are likely to occur, and the block copolymer and the PET molded product are likely to interact with each other, so that the reforming effect is more efficient and higher. Can be obtained. When the solvent of the copolymer solution contains an ester solvent, the reforming temperature is preferably 200 ° C. or lower, more preferably 190 ° C. or lower, 180 ° C. or lower, and 170 ° C. or lower in that order. If the reforming temperature is too high, depending on the shape of the PET molded body or the like, the PET molded body itself may be thermally deteriorated or deformed, and the strength of the PET molded body itself may decrease. Even when the reforming temperature is high, the influence of the temperature may be limited by shortening the contact time, and reforming may be performed.

(I) When the ester solvent contains an ester solvent having a boiling point of 150 ° C. or higher at 1 atm, the copolymer solution and PET molding are carried out in the above range of 80 ° C. to 200 ° C. (particularly 120 ° C. to 200 ° C.). It is preferable to bring it into contact with the body.

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 product in the above range of 80 ° C. to 200 ° C. (particularly, 120 ° C. to 200 ° C.). ..

When the solvent of the copolymer solution contains an aprotic polar solvent having a dielectric constant of 30 or more, the reforming temperature is preferably 120 ° C. or lower, in the order of 100 ° C. or lower, 90 ° C. or lower, 80 ° C. or lower, 70 ° C. or lower. Is more preferable. Since the aprotic polar solvent having a dielectric constant of 30 or more easily erodes the surface of the PET molded body, the higher the reforming temperature, the more likely the strength of the PET molded body itself to decrease. Although the contact time may be shortened to minimize the influence of temperature and the PET molded product itself may be modified while suppressing a decrease in strength, it is necessary to control the temperature and time more accurately. The operation may be complicated. By setting the temperature to 120 ° C. or lower, it is possible to modify the PET molded product itself while suppressing a decrease in strength with a simpler operation. When the solvent of the copolymer solution contains an aprotic polar solvent having a dielectric constant of 30 or more, the reforming temperature is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, and more preferably 30 ° C. or higher. If the reforming temperature is too low, the surface of the PET molded product is less likely to loosen or swell, and the block copolymer and the PET molded product are less likely to interact with each other. Therefore, the lower the reforming temperature, the less the reforming effect. It tends to be enough.

In particular, when the aprotic polar solvent having a dielectric constant of 30 or more contains dimethyl sulfoxide and / or N-methyl-2-pyrrolidone, the copolymer solution and the PET molded product can be used in the above range of 20 ° C to 120 ° C. It is preferable to bring them into contact with each other.

For contact at the above-mentioned predetermined temperature, the copolymer solution may be brought into contact with the PET molded product at a predetermined temperature in advance. When the reforming temperature is about room temperature (25 ° C.) or higher, the PET molded product may be brought into contact with the copolymer solution at about room temperature and then heated to raise the temperature to a predetermined temperature. Further, the copolymer solution may be quickly removed after contacting at a predetermined temperature, or cooling or slow cooling may be performed while the copolymer solution and the PET molded product are in contact with each other.

The treatment time for contacting the copolymer solution and the PET molded body can be appropriately determined according to the contact method, the composition of the copolymer solution, the shape of the PET molded body, and the like. For example, in the method of immersing the PET molded product in the copolymer solution, the immersion time is 1 second or more when the reaction between the block copolymer and the PET molded product is increased by raising the reforming temperature. It may be relatively short, such as 10 seconds or more and 30 seconds or more. Further, in order to sufficiently form the functional layer, the immersion time may be 1 minute or more or 5 minutes or more. The immersion time may be long, 60 minutes or less, or 40 minutes or less as long as the PET molded product is not deformed. Further, since the contact between the block copolymer and the PET molded product is saturated after a certain period of time, the modification effect may be 30 minutes or less or 20 minutes or less depending on the conditions such as the modification temperature.

After the contact step is completed, it may be used as it is as a modified PET molded product, or it may be further processed and used.

After the contact step, there may be a solvent removing step of removing the solvent of the coating film of the copolymer solution provided on the PET molded product, depending on the use of the modified PET molded product, or as it is. Further processing may be performed.
As a method for removing the solvent, it may be dried at around room temperature in a well-ventilated environment, or may be appropriately subjected to vacuum drying, heat drying, or the like. These drying methods may be used in combination.
Further, it may be dried after washing with a solvent having a lower boiling point that is compatible with the solvent of the copolymer solution.

<Modified polyethylene terephthalate molded product>
The present invention has 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, and the side chain crystalline block copolymer is formed. The first polymerization block, which is a repetition of the structural unit in which the side chain crystalline block copolymer has an alkyl group having 8 or more carbon atoms in the side chain, and the second, which is a repetition of the structural unit having a functional group. It relates to a modified polyethylene terephthalate molded product (hereinafter, may be referred to as “modified PET molded product of the present invention”) including a polymerization block.

Since the modified PET molded product of the present invention has a functional layer containing a block copolymer on at least a part of the surface of the PET molded product, the functionality of the block copolymer is imparted.

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

As described above, the PET molded product can be a molded product such as a film, a plate, particles, fibers, or a porous material.

As described above, the functional groups of the block (B) of the block copolymer include an amino group, an ammonium group, a carboxyl group, a hydroxyl group, a sulfonic acid group, an alkoxy group, an oxylanyl group, an oxyalkylene group, a carbonyl group and an ether group. , A polar group such as a sulfonyl group, an ester group and an amide group. It is known that having a polar group on the surface can exhibit functionality such as hydrophilicity and adhesiveness. By using the production method of the present invention to modify the surface of the PET molded body with the block copolymer containing the block (B) having the polar group as described above, the block copolymer and the PET molded body are strongly strengthened. It can be adhered to form a modified PET molded product having excellent functionality such as hydrophilicity, adhesiveness, dyeability, and metal ion adsorption.

Specifically, by modifying the surface of the PET molded body with a block copolymer containing the block (B) having an amino group, the modified PET molded body has an amino group on the surface. This makes it possible to obtain a modified PET molded product having functionality such as hydrophilicity, adhesiveness, dyeability, and metal ion adsorption.

By modifying the surface of the PET molded body with a block copolymer containing the block (B) having an oxyalkylene group, the modified PET molded body has an oxyalkylene group on the surface. This makes it possible to obtain a modified PET molded product having functionality such as hydrophilicity and adhesiveness.

By modifying the surface of the PET molded body with the block copolymer containing the block (B) having a carboxyl group, the modified PET molded body has a carboxyl group on the surface. This makes it possible to obtain a modified PET molded product having functionality such as adhesiveness.

The functional machine of the block (B) of the block copolymer is preferably selected from the group consisting of an amino group, an ammonium group, a carboxyl group, a hydroxyl group, a sulfonic acid group, and an oxylanyl group, and an amino group and a carboxyl group are preferable. Alternatively, an oxyalkylene group is more preferable.

In the modified PET molded product, the block copolymer preferably contains a block (B) having an amino group, a carboxyl group or an oxyalkylene group in the side chain, and is more preferably the following (p1) to (p3). preferable.
(P1) A block copolymer (p2) 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. ) 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). Block Polymer (p3) 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 (meth) acrylic acid.

The block copolymer constituting the modified PET molded product preferably has a block (A) having a molecular weight of 3,000 or more and a block (B) having a molecular weight of 500 or more. By having such a molecular weight, the PET molded product and the block copolymer can be stably adhered to each other. It is more preferable that the block (A) has a molecular weight of 5,000 or more, the block (B) has a molecular weight of 1,000 or more, and the block (A) has a molecular weight of 5,000 or more. It is more preferable that the molecular weight of the block (B) is 5,000 or more.

The functional layer containing the side-chain crystalline block copolymer may be formed at a site where the functionality of the side-chain crystalline block copolymer is required, depending on the use of the modified PET molded product of the present invention. The range can be adjusted as appropriate. The functional layer may be formed on the entire surface of the PET molded product, or may be formed on the surface of the PET molded product in a layered shape, a mottled shape, a striped shape, or the like. Further, if the PET molded product is a porous material such as a porous film, a functional layer may be formed not only on the surface but also in the pores.

The molded product of the present invention can be confirmed by a method such as component analysis of each layer by FT-IR or the like, or component analysis of the cut surface.

In the modified PET molded product 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 product of the present invention can be produced by the method for producing the modified PET molded product of the present invention, and in the production thereof, the copolymer solution and the PET molded product are brought into contact with each other. .. After the contact between the copolymer solution and the PET molded body, the solvent of the copolymerized solution provided in the PET molded body may be used without being removed, or even if the solvent is removed, the solvent may not be completely removed and remains.

For example, the modified PET molded product of the present invention can be a molded product having excellent adhesiveness, and the peel strength on the surface of the functional layer is 0.1 N / mm or more, 0.5 N / mm or more, 0. It is also possible to make a molded product of .7 N / mm or more and 1.0 N / mm or more. The peel strength can be calculated by a T-type peel test described later, and can be calculated as a value obtained by dividing the maximum test force by the length in the width direction of the test piece. Further, the reforming temperature or the like may be adjusted so that a molded product having a peel strength of 5.0 N / mm or less or 3.0 N / mm or less on the surface of the functional layer may be used.

The modified PET molded product of the present invention has the characteristics of a side chain crystalline block copolymer. This can be used for conventional applications of PET molded products, and it is expected that the applications will be expanded by utilizing the modified properties thereof.

Further, even if the surface of the PET molded body is modified with the block copolymer, if the adhesion between the block copolymer and the PET molded body is weak, the functionality based on the block (B) of the block copolymer can be sufficiently obtained. It is considered difficult to express. By using the production method of the present invention, the PET molded product and the block copolymer can be strongly adhered to each other, and a modified PET molded product having excellent surface characteristics based on the block (B) can be obtained. can.

The adhesive strength between the PET molded product and the block copolymer can be indexed by the peel strength. One of the preferred modified PET molded products of the present invention has a polyethylene terephthalate molded product and a functional layer containing a side chain crystalline block copolymer formed on at least a part of the surface of the molded product. The side chain crystalline block copolymer is selected from the group consisting of (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin and substituted styrene having an alkyl group having 8 or more carbon atoms. It contains a first polymerization block (block (A)) which is a polymer of any of the monomers and a second polymerization block (block (B)) which is a repetition of a structural unit having a polar group in the side chain. It is a modified PET molded product (hereinafter, may be referred to as a modified PET molded product (M1)) having a peeling strength of the functional layer of 0.5 N / mm or more. It was

If the structure is similar to that of the modified molded product (M1), the functionality based on the block (B) of the block copolymer can be sufficiently exhibited. 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.

Further, the strength of adhesion between the PET molded body and the block copolymer can be used as an index of the surface state of the modified molded body after the good solvent of the block copolymer and the modified molded body are brought into contact with each other. .. In the modified PET molded product of the present invention, even after the modified PET molded product is brought into contact with a good solvent of the block copolymer, the block copolymer is not detached and the portion containing the block copolymer is contained. It can remain on the surface. For example, even after the modified PET molded product was brought into contact with butyl acetate at 55 ° C. (for example, contact for 1 minute), the block copolymer did not desorb and the portion containing the block copolymer remained on the surface. Can be.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless the gist thereof is changed.

<Evaluation>
For gel permeation chromatography (GPC) measurement, HLC-8320GPC, EcoSEC (manufactured by Tosoh Corporation) was used.
A Spectrum Two (manufactured by PerkinElmer Japan Co., Ltd.) was used for the measurement of the IR spectrum.

<Evaluation of adhesiveness of modified PET film>
A T-type peeling test was performed according to JIS K6854-3 (1999), the peeling strength was calculated, and the adhesiveness was evaluated. As the test apparatus, a small desktop tester EZ-test EZ-LX manufactured by Shimadzu Corporation was used. As the test piece, two PET films (modified PET films) modified under the same conditions were bonded together using a cyanoacrylate adhesive (product name: Aron Alpha (registered trademark) 201, manufactured by Toagosei Co., Ltd.). (Width 12.5 mm, adhesive portion length 75 mm, non-adhesive portion length 25 mm) were used (see FIG. 1 (a)).

(Peeling test)
The test was conducted in a constant temperature and humidity chamber at 25 ° C., 1 atm and 50% humidity. The non-adhesive portions of the test pieces were arranged in the T-shape, and each of them was gripped by the gripping tool of the test device and pulled in the direction of separation at 10 mm / min to measure the adhesive force. The test was performed 3 to 8 times under each condition.

The peel strength [N / mm] is a value obtained by dividing the maximum test force [N] by the width [mm] of the test piece. As shown in FIG. 1 (b), the result of 12.5 mm immediately after the start of each peeling test was cut out, and the maximum test force was obtained from the remaining result. The peel strength was calculated using this maximum test force. Further, when the test piece started to break immediately after the start of the test (Stroke was within 0 to 12.5 mm) due to strong adhesion, the peel strength was calculated using the maximum test force calculated from all the data. The peel strength was calculated as the average of all the tests regardless of the presence or absence of breakage of the modified PET film itself during the peel test.

The evaluation results of the adhesiveness of the modified film are shown in FIGS. 3 to 10. In FIGS. 3 to 10, the white column means that the modified PET film itself was not destroyed during the peeling test, and all the test pieces were peeled off, and the black column means that the modified PET film itself was peeled off during the peeling test. It means that the test piece destroyed by is also included. Details of the modification conditions and evaluation results of each modified film will be described later.

<Manufacturing of side chain crystalline block copolymer (SCCBC)>
[reagent]
Stearyl acrylate (STA) was used as the monomer (a), and 2- (tert-butylamino) ethyl methacrylate (TBAEMA) was used as the monomer (b). These monomers were used after removing the stabilizer using an inhibitor remover (manufactured by Sigma-Ardrich).
BlocBuilder (registered trademark) MA (manufactured by Arkema) was used as a polymerization initiator.

[Manufacturing]
According to the following polymerization scheme, stearyl acrylate and 2- (tert-butylamino) ethyl methacrylate were polymerized by living radical polymerization (NMP method). After the polymerization was stopped, it was reprecipitated with methanol and vacuum dried to obtain a block copolymer (1) (STA-TBAEMA).

When the IR spectrum of the obtained block copolymer (1) was measured, the absorption peak derived from C = O of the ester, the absorption peak derived from the CH stretching vibration of the alkyl chain of STA, and the CH stretching vibration of TBAEMA were measured. Absorption peaks derived from vinyl bonds were observed, while absorption peaks derived from vinyl bonds were not observed. From this, it was judged that the block copolymer was successfully polymerized.

Further, when the molecular weight of the block copolymer (1) was estimated from GPC, the Mw (weight average molecular weight g / mol) of STA was 8,000, and the TBAEMA (weight average molecular weight g / mol) was 8,000. rice field.

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

[Preparation of copolymer solution (SCCBC solution)]
As shown in Table 1, the block copolymer (1) was dissolved in a solvent to obtain solutions (S1) to (S7) having the compositions shown in Table 1.

[Examples 1 to 5, Comparative Example 1 to Comparative Example 4]
The PET film was immersed in the warmed solution (s1) for 10 minutes. Then, the PET film taken out from the solution (s1) was immersed in butyl acetate at 25 ° C. and washed with stirring for 1 minute. Then, it was air-dried for one day to obtain a modified PET film.
The temperature of the solution (reform temperature) in each example is as shown in Table 2.
In Comparative Example 1, the PET film was used as it was without modification. Further, the treatment was carried out using the solution or solvent shown in Table 2 under the modification conditions shown in Table 2 to obtain comparative PET films of Comparative Examples 2 to 4.

(Confirmation of SCCBC on PET film)
FIG. 2 shows the measurement results of the IR spectrum on the surface of the modified PET film obtained in Example 5. Since the peak appeared near 3000 cm ^-1 , the presence of SCCBC could be confirmed on the PET surface.

(Temperature dependence)
A peeling test was performed using the modified PET films of Examples 1 to 5 and the comparative PET films of Comparative Examples 1 to 4, and the adhesiveness was evaluated. In addition, the peeling test was performed 7 times in Examples 1 to 3, the peeling test was performed 8 times in Examples 4 and 5, and the peeling test was performed 5 times in Comparative Examples 1 to 4, and each of them averaged. The peel strength was calculated.
3 and 2 show the results of the evaluation of the adhesiveness of Examples 1 to 5, Comparative Example 1 and Comparative Example 2.
As shown in FIGS. 3 and 2, PET modified with the solution (s1) (STA-TBAEMA, DEP) at 80 ° C. (Example 1) adheres more than unmodified PET (Comparative Example 1). The force (peeling strength) has improved. Further, as the reforming temperature was raised, the adhesive strength was greatly improved as compared with the unmodified PET. At 100 ° C, 1 out of 7 samples, at 140 ° C, 3 out of 8 samples, and at 160 ° C, 7 out of 8 samples showed breakage of the PET film itself, confirming that the adhesiveness was very excellent.

(Effect of solvent)
4 and 2 show the results of the evaluation of the adhesiveness of Example 4, Example 5, Comparative Example 3 and Comparative Example 4.
As shown in FIG. 4, in Examples 4 and 5 immersed in the solution (s1) (STA-TBAEMA, DEP), the adhesive strength was improved as compared with the unmodified PET of Comparative Example 1. On the other hand, in Comparative Examples 3 and 4 immersed only in diethyl phthalate, no improvement in the adhesive strength was observed, which was equivalent to the adhesive strength of the unmodified PET of Comparative Example 1. From this, it was confirmed that the improvement of the adhesive strength was due to SCCBC.

[Examples 3-A to 3-E, Examples 4-A to 4-D]
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.
Further, 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.

(Dependence of immersion time)
The peeling test was performed 5 times using the modified PET films of Examples 3-A to 3-E, and the adhesiveness was evaluated. 5 and 3 show the results of the evaluation of the adhesiveness of Examples 3 and 3-A to 3-E.
Moreover, the peeling test was performed 5 times using the modified PET films of Examples 4-A to 4-D, and the adhesiveness was evaluated. 6 and 4 show the results of the evaluation of the adhesiveness of Examples 4 and 4-A to 4-D.

As shown in FIGS. 5 and 6, the adhesive strength improved as the immersion time became longer, and the number of samples destroyed by the PET film itself tended to increase in the peeling test. At 120 ° C., the PET film itself was destroyed in 1 out of 5 samples by immersion for 30 minutes. The PET film itself was destroyed in 3 out of 5 samples by soaking for 1 hour. At 140 ° C., the PET film itself was destroyed in 2 out of 5 samples by immersion for 1 minute and 5 minutes. The PET film itself was destroyed in 4 out of 5 samples by the immersion time of 30 minutes. In addition, in the immersion at 140 ° C. for 10 minutes, as described above, the PET film itself was destroyed in 3 out of 8 samples. Further, the higher the reforming temperature, the higher the reforming effect was obtained in a shorter time.

[Examples 5-A to 5-C]
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.

(Dependence on the concentration of the copolymer solution)
The peeling test was performed 5 times using the modified PET films of Examples 5-A to 5-C, and the adhesiveness was evaluated. 7 and 5 show the results of the evaluation of the adhesiveness of Examples 5 and 5-A to 5-C.
As shown in FIG. 7, the adhesive strength was improved as compared with the unmodified PET in any case regardless of the concentration of SCCBC. At a concentration of SCCBC of 0.01 wt% (Example 5-A), 1 sample out of 5 samples had a concentration of SCCBC of 0.5 wt% (Example 5-B) and a concentration of SCCBC of 1.0 wt% (Example 5-C). ), The PET film itself was destroyed in all 5 samples out of 5 samples.

[Examples 5-a to 5-d]
Modified PET of Examples 5-a to 5-d in the same manner as in Example 5 except that the cleaning conditions with butyl acetate after removing the PET film from the SCCBC solution were changed to the conditions shown in Table 6. I got a film.

(Effect of washing with butyl acetate after modification)
The peeling test was performed three times using the modified PET films of Examples 5-a to 5-d, and the adhesiveness was evaluated. 8 and 6 show the results of the evaluation of the adhesiveness of Examples 5 and 5-a to 5-d.
As shown in FIG. 8, no significant change was observed in the adhesive strength in any of the cases. Further, in Examples 5-a to 5-d, the PET film itself was destroyed in all 3 samples out of 3 samples. Therefore, it was found that washing with butyl acetate had almost no effect on the adhesive strength of the modified PET film at about room temperature.

[Reference Example 6]
The PET film was immersed in a solution (s5) (STA-TBAEMA, xylene) heated to 120 ° C. for 10 minutes. The PET film was taken out from the solution (s5) and air-dried for one day to obtain a modified PET film.
When the peeling test was performed 5 times using the modified PET film of Reference Example 6 and the adhesiveness was evaluated, the peeling strength was 0.13 [N / mm]. Since the boiling point of xylene is about 140 ° C, it is difficult to heat it to 120 ° C or higher, and it is expected that the modification effect will be improved by using diethyl phthalate, which is easier to treat at a higher temperature than xylene. ..

[Examples 7-A to 7-F]
The PET film was immersed in the warmed solution (s6) (STA-TBAEMA, NMP) for 10 minutes. Then, the PET film taken out from the solution (s6) was immersed in butyl acetate at 25 ° C. and washed with stirring for 1 minute. Then, it was dried to obtain a modified PET film.
The temperature (reform temperature) and drying conditions of the solution in each example are as shown in Table 7.
Further, in Comparative Example 5, treatment was performed using NMP (solvent only) instead of SCCBC under the reforming temperature and drying conditions shown in Table 7.

The peeling test was performed 5 times using the modified PET films of Examples 7-A to 7-F, and the adhesiveness was evaluated. 9 and 7 show the results of the evaluation of the adhesiveness of Examples 7-A to 7-F, Comparative Examples 1 and 5.
As shown in FIGS. 9 and 7, PET modified with the solution (s6) (STA-TBAEMA, NMP) was treated with unmodified PET (Comparative Example 1) and PET treated with NMP (solvent only) (PET (solvent only). The adhesive strength (peeling strength) was improved as compared with Comparative Example 5). All of the modified PET films (Examples 7-A to 7-F) showed breakage of the PET film itself, and it was confirmed that the adhesiveness was very excellent. NMP has improved adhesive strength when modified at a lower temperature than diethyl phthalate.

[Examples 8-A to 8-C]
The PET film was immersed in the warmed solution (s7) (STA-TBAEMA, DMSO) for 10 minutes. Then, the PET film taken out from the solution (s7) was immersed in butyl acetate at 25 ° C. and washed with stirring for 1 minute. Then, it was dried to obtain a modified PET film.
The temperature (reform temperature) and drying conditions of the solution in each example are as shown in Table 8.
Further, in Comparative Example 6, DMSO (solvent only) was used instead of SCCBC, and the treatment was performed at the reforming temperature and the drying conditions shown in Table 8.

The peeling test was performed 5 times using the modified PET film of Examples 8-A to 8-C and the comparative PET film of Comparative Example 6 to evaluate the adhesiveness. 10 and 8 show the results of the evaluation of the adhesiveness of Examples 8-A to 8-C, Comparative Examples 1 and 6.
As shown in FIGS. 10 and 8, PET modified with the solution (s7) (STA-TBAEMA, DMSO) was treated with unmodified PET (Comparative Example 1) and PET treated with DMSO (solvent only) (PET (solvent only). The adhesive strength (peeling strength) was improved as compared with Comparative Example 6). All of the modified PET films (Examples 8-A to 8-C) showed breakage of the PET film itself, and it was confirmed that the adhesiveness was very excellent. DMSO has improved adhesive strength when modified at a lower temperature than diethyl phthalate.

According to the present invention, it is possible to impart adhesiveness to polyethylene terephthalate by utilizing the characteristics of the side chain crystalline block copolymer, and it is expected that polyethylene terephthalate will be applied in new applications.

Claims

It has a contact step of bringing a copolymer solution containing a side chain crystalline block copolymer and a solvent into contact with a polyethylene terephthalate molded product.
The side chain crystalline block copolymer is a first polymerization block in which a structural unit having an alkyl group having 8 or more carbon atoms in the side chain is repeated, and a second polymer in which the structural unit has a functional group is repeated. Including polymerization blocks
A method for producing a modified polyethylene terephthalate molded product, wherein the solvent comprises the following (i) or (ii).
(I) Ester-based solvent having a boiling point of 150 ° C. or higher at 1 atm (ii) Aprotic polar solvent having a dielectric constant of 30 or higher.
The ester solvent contains a phthalate ester compound and contains
The method for producing a modified polyethylene terephthalate molded product according to claim 1, wherein in the contact step, the copolymer solution and the polyethylene terephthalate molded product are brought into contact with each other at 80 ° C. or higher.
The production method according to claim 2, wherein the phthalate ester compound is selected from the group consisting of dimethyl phthalate, diethyl phthalate, and dioctyl phthalate.
The manufacturing method according to claim 2 or 3, wherein the contact is at 120 ° C. or higher and 200 ° C. or lower.
The aprotic polar solvent having a dielectric constant of 30 or more contains dimethyl sulfoxide and / or N-methyl-2-pyrrolidone.
The method for producing a modified polyethylene terephthalate molded product according to claim 1, wherein in the contact step, the copolymer solution and the polyethylene terephthalate molded product are brought into contact with each other at 20 ° C. or higher and 120 ° C. or lower.
The first polymerization block is selected from the group consisting of (meth) acrylate, (meth) acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin and substituted styrene having an alkyl group having 8 or more carbon atoms. The production method according to any one of claims 1 to 5, which is a polymer of the monomer of.
The production method according to any one of claims 1 to 6, wherein the second polymerization block is a repetition of a structural unit having a polar group in the side chain.
It has a polyethylene terephthalate molded product and a functional layer containing a side chain crystalline block copolymer formed on at least a part of the surface of the molded product.
The side chain crystalline block copolymer is a first polymerization block in which a structural unit having an alkyl group having 8 or more carbon atoms in the side chain is repeated, and a second polymer in which the structural unit has a functional group is repeated. Including polymerization blocks
The peel strength of the functional layer in the T-type peel test is 0.5 N / mm or more.
Modified polyethylene terephthalate molded product.
The modified polyethylene terephthalate molded product according to claim 8, wherein the second polymerization block is a repetition of a structural unit having a polar group in the side chain.
The modified polyethylene terephthalate molded product according to any one of claims 8 or 9, wherein the second polymerization block is a repetition of a structural unit having an amino group, a carboxyl group or an oxyalkylene group in a side chain.
The weight average molecular weight of the first polymerization block is 5,000 or more, and the weight average molecular weight is 5,000 or more.
The modified polyethylene terephthalate molded product according to any one of claims 8 to 10, wherein the second polymerization block has a weight average molecular weight of 5,000 or more.
The modification according to any one of claims 8 to 11, wherein the site containing the side chain crystalline block copolymer remains on the surface even after contact with a good solvent of the side chain crystalline block copolymer. Polyethylene terephthalate polymer.
A copolymer solution containing a side chain crystalline block copolymer and a solvent.
The side chain crystalline block copolymer includes 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 in which the solvent comprises the following (i) or (ii).
(I) Ester-based solvent having a boiling point of 150 ° C. or higher at 1 atm (ii) Aprotic polar solvent having a dielectric constant of 30 or higher.