JP7625239B2 - Molded article containing side-chain crystalline block copolymer and method for producing same - Google Patents

Description

The present invention relates to a molded article containing a side-chain crystalline block copolymer and a method for producing the same.

Many thermoplastic resins, such as polyolefin resins, have been molded to suit a variety of applications and put to practical use. Molded bodies of these resins have different physical properties depending on the nature of the respective resins. There are cases where these molded bodies are required to have specific physical properties, such as adhesiveness, on their surfaces. To modify the surfaces of these molded bodies of resins, plasma treatment, corona treatment, flame treatment, UV irradiation, and the like have been used to impart adhesiveness to the surface. However, such treatments require special equipment, and the effects may be limited to a short period of time.

As a method for modifying such resin molded bodies, the present inventors have proposed a method using a side-chain crystalline block copolymer (SCCBC) that has a block with a long alkane chain in the side chain and a functional block that exhibits various functions (Patent Documents 1 to 3, Non-Patent Document 1).

For example, Patent Document 1 relates to a surface modification material comprising a substrate at least a part of which is polyethylene and a polymer that modifies the surface of the polyethylene, the polymer being a block copolymer of monomers including a first monomer that is an acrylate having an alkane chain having 10 or more carbon atoms in length and a second monomer that is an acrylate of a tertiary amine, or a block copolymer of monomers including a first monomer that is a (meth)acrylate having an alkane chain having 10 or more carbon atoms in length and a second monomer that is a (meth)acrylate having a side chain having 4 or more carbon atoms and a -CF ₂ - structure. Specifically, a method of modifying the surface of a substrate with a surface modification composition is disclosed, in which the surface modification composition is attached to the surface of the substrate by, for example, a dipping method or a coating method, and then the dispersion medium is removed.

Patent Document 2 discloses a method for modifying a polyethylene-based resin molded product, which includes the steps of: preparing a copolymer solution by dissolving a copolymer for modifying polyethylene, the copolymer having a structure derived from a first monomer (A) and a structure derived from a second monomer (B), the monomer (A) being a monomer having an alkane chain with a length of 8 carbon atoms or more in its side chain, and the monomer (B) being a monomer having a specific fluorinated alkyl group in its side chain, in a solvent; bringing the copolymer solution into contact with a polyethylene-based resin molded product; and forming the copolymer layer on the surface of the molded product by volatilizing the solvent of the copolymer solution brought into contact with the molded product.

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

Patent No. 6445258 JP 2018-030927 A JP 2019-137779 A

Journal of Adhesion Science and Technology, 2019, 33, 2567-2578.

Patent Documents 1 to 3 disclose methods that use a solution or dispersion in which a side-chain crystalline block copolymer is dissolved or dispersed in a solvent. These methods can modify the properties of resin molded bodies, but require coating or immersion in a solvent.

When using a solvent, a coating or immersion process is required, and a drying process is also required, but there are also environments and products where the use of solvents is restricted. Furthermore, only the surface that can come into contact with the solution or dispersion is modified. In order to increase the freedom of manufacturing conditions, new methods that can obtain modified molded bodies are also required.

In this situation, the object of the present invention is to provide a molded body with a modified surface layer or a layer near the surface, and a method for producing the same.

As a result of intensive research aimed at solving the above problems, the inventors discovered that the following invention meets the above objective, and thus arrived at the present invention. That is, the present invention relates to the following inventions.

<1> A method for producing a molded article, comprising melt-molding a kneaded resin obtained by kneading a thermoplastic resin and a side-chain crystalline block copolymer, thereby modifying a surface layer of the molded article.
<2> The thermoplastic resin is one or more resins selected from the group consisting of polyolefin-based resins, polyester-based resins, polystyrene-based resins, and polyacrylic resins,
The method for producing a molded article according to <1>, wherein the content of the side chain crystalline block copolymer in the kneaded resin (mass of side chain crystalline block copolymer/mass of kneaded resin) is 0.05 to 10.0 mass%.
<3> The method for producing a molded article according to <1> or <2>, wherein the side chain crystalline block copolymer includes a first polymer block which is a repeat of a structural unit having an alkyl group having 8 or more carbon atoms in a side chain, and a second polymer block which is a repeat of a structural unit having a functional group.
<4> The method for producing a molded article according to <3>, wherein the functional group is a polar group and/or a functional group having a metal adsorption ability.
<5> The first polymer block is a polymer of any one monomer (A) selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, the monomer having an alkyl group having 8 or more carbon atoms,
The method for producing a molded article according to <3> or <4>, wherein the second block is a polymer of any one of monomers (B) selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, the monomer having any one of groups selected from the group consisting of an amino group, an amide group, a sulfo group, an oxyalkylene group, and an oxiranyl group.
<6> A thermoplastic resin and a side chain crystalline block copolymer are contained,
a surface layer having a portion where the side chain crystalline block copolymer is selectively distributed and arranged;
a surface-nearby layer in contact with the surface layer and having a portion containing the side-chain crystalline block copolymer.

The manufacturing method of the present invention allows for the production of a molded article with a modified surface layer. In addition, the molded article of the present invention has a surface layer or a layer near the surface that contains a side-chain crystalline block copolymer, and has modified physical properties.

FIG. 2 is a diagram showing an example of a molding apparatus used for producing a raw material for the molded body of the present invention. FIG. 2 is a diagram showing another example of a molding apparatus used for producing a molded article of the present invention.

The following describes in detail the embodiment of the present invention, but the description of the constituent elements described below is one example (representative example) of the embodiment of the present invention, and the present invention is not limited to the following content as long as the gist of the present invention is not changed. Note that when the expression "~" is used in this specification, it is used as an expression including the numerical values before and after it.

[Method of manufacturing the molded article of the present invention]
The method for producing a molded article of the present invention is a method for producing a molded article in which a kneaded resin obtained by kneading a thermoplastic resin and a side-chain crystalline block copolymer is melt-molded to modify the surface layer of the molded article.
According to the method for producing a molded article of the present invention, a molded article having a modified surface layer can be obtained. This production method does not require treatment with a solvent or the like, and can produce a molded article having a modified surface layer molded into any shape.

[Molded article of the present invention]
The molded article of the present invention has a surface layer that contains a thermoplastic resin and a side-chain crystalline block copolymer and has a portion where the side-chain crystalline block copolymer is selectively distributed and arranged unevenly, and a surface-nearby layer that is in contact with the surface layer and has a portion containing the side-chain crystalline block copolymer.

The molded body of the present invention can be manufactured by the manufacturing method of the molded body of the present invention, and the corresponding configurations in this application can be used interchangeably.

The present inventors have investigated the use of side-chain crystalline block copolymers to modify the surface layer or the layer near the surface of a thermoplastic resin. Thermoplastic resins are melt-molded by injection molding, extrusion molding, or the like. The thermal history during this melt molding is a high-temperature process, and it is necessary to take into consideration factors such as heat resistance and behavior when heated, and it is thought that there are limitations to what can be mixed.

When modifying various molded products with side-chain crystalline block copolymers, they have been used in a dissolved/dispersed state in a solvent. In this case, a relatively small amount of side-chain crystalline block copolymer is used because it is directly applied to the surface. However, when used in molding involving melt-kneading of a thermoplastic resin composition, a considerably large amount may be required, taking into account the amount that is uniformly dispersed and remains on the surface. On the other hand, there is a concern that micellization, in which the side-chain crystalline block copolymers self-aggregate, may occur when a large amount of side-chain crystalline block copolymer is mixed. When micellization occurs, the physical properties that are mainly contributed by the inner layer of the molded product, change significantly, making it unsuitable for the original use or making it impossible to obtain a molded product.

Assuming this would occur, the inventors mixed a relatively small amount of a side-chain crystalline block copolymer into a thermoplastic resin and performed melt molding. They found that the side-chain crystalline block copolymer could be selectively distributed in the surface layer or the layer near the surface, with little effect on the inner layer, and that the surface layer or the layer near the surface could be modified. In addition, the side-chain crystalline block copolymer does not precipitate completely on the surface, and part of its structure has a high affinity with the thermoplastic resin, so it is believed that a phenomenon similar to anchoring occurs in which the side-chain crystalline block copolymer is arranged toward the inner layer of the molded body, resulting in a stable modification effect. The present invention is based on this finding.

[Thermoplastic resin]
The molded article in the present invention is a molded article of a resin composition containing a thermoplastic resin as a main component. The thermoplastic resin is a resin that exhibits plasticity when heated. The thermoplastic resin may be any resin that is molded into a state having fluidity by heating, such as injection molding or extrusion molding. The resin composition is a composition that contains such a thermoplastic resin as a main component.

The resin composition may contain 50% by mass or more of thermoplastic resin. Depending on the type of thermoplastic resin, the use of the molded body, other mixtures, etc., the proportion of thermoplastic resin in the resin composition may be 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more.

The resin composition contains at least a side-chain crystalline block copolymer as a component other than the thermoplastic resin. In addition to these, the resin composition may contain various components contained in a molded product using the resin composition.

Thermoplastic resins that can be used include, for example, polyolefin resins, polyester resins, polystyrene resins, and polyacrylic resins. In particular, it is preferable that the thermoplastic resin is hydrophobic. Thermoplastic resins that contain multiple types of resins may be used.

The thermoplastic resin is particularly preferably a polyolefin resin. A polyolefin resin is a crystalline polymer obtained by polymerization of an α-olefin having a double bond at the 1-position, such as polyethylene resin or polypropylene resin. Examples of polyolefin resins include polyethylene resin and polypropylene resin. Resins made mainly of polyethylene are sometimes called polyethylene resins, and those made mainly of polypropylene are sometimes called polypropylene resins.

These thermoplastic resins may be recycled resins. Recycled resin is a general term for pre-consumer products such as waste and defective products generated in the process of molding a thermoplastic resin composition from virgin pellets, and resins that are distributed on the market as molded products such as recycled plastic containers and packaging (so-called "container replastics") and then discarded after consumption. An example of such a recycled resin is recycled polyolefin resin, such as polyethylene resin or polypropylene resin manufactured (regenerated) from container and packaging plastic.

Polyester resins are polycondensates synthesized by dehydrating and condensing polycarboxylic acids and polyalcohols to form ester bonds. Examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane dimethylene terephthalate, and polyethylene naphthalate (PEN).

Polystyrene resins are polymers that are polymerized using styrene derivatives as monomers.

Polyacrylic resins are polymers that are polymerized using acrylic acid esters or methacrylic acid esters as monomers. For example, PMMA (polymethyl methacrylate) is one example.

[Side Chain Crystalline Block Copolymer]
A side-chain crystalline block copolymer is a block copolymer of a polymer having a structure exhibiting crystallinity in the side chain and a polymer having a structure exhibiting a modifying effect, and is a copolymer that can form a site in a thermoplastic resin where a part of this block copolymer interpenetrates.

The side-chain crystalline block copolymer includes a first polymerization block which is a repeating structural unit having an alkyl group (alkane chain) having 8 or more carbon atoms in the side chain, and a second polymerization block which is a repeating structural unit having a functional group. The first polymerization block can be a polymerized monomer (A), and the second polymerization block can be a polymerized monomer (B), and the copolymers thereof can be used.

The monomer (A) is preferably any monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, which has an alkane chain having 8 or more carbon atoms in its side chain, and the monomer (B) is preferably a monomer having a functional group.
In addition, the copolymer may be a block copolymer having a polymerization block derived from monomer (A), which is a portion formed by polymerization of monomer (A), and a polymerization block derived from monomer (B), which is a portion formed by polymerization of monomer (B).

In side-chain crystalline block copolymers, the structure derived from monomer (A) is sometimes called "block (A)" and the structure derived from monomer (B) is sometimes called "block (B)."

The side-chain crystalline block copolymer used in this application may be one that references the side-chain crystalline block copolymers disclosed in Japanese Patent No. 6445258, JP-A No. 2018-030927, JP-A No. 2019-137779, JP-A No. 2018-080329, etc.

[Monomer (A)]
The monomer (A) is preferably any monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, which has an alkane chain having 8 or more carbon atoms in its side chain. By using this monomer (A), the side chain crystalline block copolymer has a structural unit (A) derived from the monomer (A).

In this application, "(meth)acrylate" means both acrylate and methacrylate. Similarly, "(meth)acrylamide" means both acrylamide and methacrylamide.

[Structural unit (A)]
The structural unit (A) is preferably a structural unit derived from a (meth)acrylate or α-olefin monomer having an alkane chain in a side chain with a length of 8 or more carbon atoms, because the alkane chain in the side chain is likely to have a structure exhibiting crystallinity and is likely to interact with the thermoplastic resin.

The structural unit (A) has an alkane chain having 8 or more carbon atoms in its side chain. Examples of the alkane chain having 8 or more carbon atoms in the side chain of the structural unit (A) 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 alkane chain in the side chain may be directly bonded to the main chain, or may be bonded to the main chain via a linking group such as an ester bond, an amide bond, an ether bond, or a benzene ring.

The structural unit (A) preferably has an alkane chain having 12 or more carbon atoms, and more preferably has an alkane chain having 16 or more carbon atoms, because this tends to exhibit crystallinity and can further improve the interaction between the copolymer and the thermoplastic resin. In addition, this alkane chain is preferably a linear alkane chain.

On the other hand, the upper limit can be appropriately set within a range that allows modification of the surface of the thermoplastic resin, taking into consideration dispersibility in the solvent during production and dispersibility during melt molding. A specific upper limit is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less in reality. If the alkane chain is too large, the copolymer may not have an appropriate three-dimensional structure, resulting in reduced interpenetration with the thermoplastic resin. In addition, it may be difficult to set the polymerization conditions for producing a side-chain crystalline block copolymer.

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

In formulae (A-1) and (A-2), R ^a1 represents a hydrogen atom or a methyl group.

In general formulas (A-1) and (A-2), R ^a2 represents an alkane chain having 8 or more carbon atoms. As described above, R ^a2 is preferably a linear alkane chain. The number of carbon atoms in the alkane chain represented by R ^a2 is preferably 12 or more, and more preferably 16 or more. The upper limit can be 50 or less, 40 or less, 30 or less, 25 or less, or the like.

From the viewpoints of ease of obtaining the monomer, ease of controlling the polymerization conditions, ease of interaction between alkane chains having 8 or more carbon atoms, etc., it is more preferable that block (A) be general formula (A-1).

In the general formulas (A-1) and (A-2), n is an integer of 2 or more. n is appropriately determined within a range in which the surface layer of a molded thermoplastic resin can be modified, depending on the length of the alkane chain in the side chain, the arrangement of the structural unit (A) and the structural unit (B), the polymerization degree of the structural unit (B), and the like. When the side chain crystalline block copolymer is a block copolymer, n is preferably 2 to 1,000, and more preferably 5 or more or 10 or more. By making it 5 or more or 10 or more, the side chain is more likely to have crystallinity, and it is possible to more stably melt-knead with the thermoplastic resin to modify the surface layer of the molded body. Furthermore, when the side chain crystalline block copolymer is a block copolymer, n may be 800 or less or 500 or less within a range in which the effects of the structural unit (A) and the structural unit (B) can be sufficiently obtained.

Specific examples of monomer (A) include hexadecyl acrylate, dodecyl acrylate (lauryl acrylate), dodecyl methacrylate (lauryl methacrylate), octadecyl acrylate (stearyl acrylate), octadecyl methacrylate (stearyl methacrylate), docosyl acrylate (behenyl acrylate), docosyl methacrylate (behenyl methacrylate), etc.

[Monomer (B)]
The monomer (B) is a monomer having a functional group. The functional group may have a polar group.

Monomer (B) may be any monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, having any one selected from the group consisting of amino group, amide group, sulfo group, oxyalkylene group, and oxiranyl group.

[Structural unit (B)]
The side chain crystalline block copolymer may have a structural unit (B) having a structure having a functional group in the side chain.

[Functional Group]
Here, the functional group is a group that exists in the copolymer after polymerization and has a function of modifying the molded article of the present invention. Examples of the functionality include hydrophilicity, ion conductivity, adhesiveness, heavy metal carrying ability, organic solvent affinity, and dyeability. The functional group is a structure corresponding to these. Representative polar groups include an amino group (-NR ₂ ), a carboxy group (-COOH), a hydroxyl group (-OH), a carbonyl group (-C=O-), an ether group (-O-), a sulfo group (-SO ₃ H), an ester group (-COO-), an amide group (-CONR ₂ -), and an oxyalkylene group (-C _n H _2n O-). These functional groups are directly bonded to the main chain or the part that becomes the main chain of (B) or are bonded via a linking group (an ester bond, an amide bond, an ether bond, a benzene ring, etc.).

[Polar group]
The side chain crystalline block copolymer can have a structural unit (B) having a structure with a polar group in the side chain. Here, the polar group is a group with a large bias in the charge distribution. By using the copolymer having a structure with these polar groups, the modified molded body has the effects of improving adhesion, improving hydrophilicity, improving dyeability, etc.

[Metal adsorption capacity]
The side chain crystalline block copolymer may have a structural unit (B) having a structure exhibiting metal adsorption ability in the side chain. Here, the metal adsorption ability means that a molecular structure that exhibits adsorption characteristics with metals or metal ions due to a polar group in the molecular structure, or that is chemically bonded to metals or metal ions or that is easily complexed is provided in the copolymer, and the structure is arranged on the surface of a molded article, thereby exhibiting the property of supporting, adsorbing, and holding metals or metal ions.

[Group of structural unit (B)]
The structural unit (B) preferably has at least one group selected from the group consisting of an amino group, an amido group, a sulfo group, an oxyalkylene group, and an oxiranyl group.

More preferably, the structure is derived from any monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, which has these structures in the side chain.

[Amino group]
The monomer (B) may have an amino group. This amino group is present as an amine in the structure of the side chain crystalline block copolymer after polymerization. Here, amine is a general term for a compound in which a hydrogen atom of ammonia is substituted with a hydrocarbon group. A compound with one substitution is called a primary amine, a compound with two substitutions is called a secondary amine, a compound with three substitutions is called a tertiary amine, and a compound with an alkyl group bonded to a tertiary amine is called a quaternary ammonium ion. These various amines are present in the side chain crystalline block copolymer as a structure derived from the monomer (B), and thus functions such as hydrophilicity, ion conductivity, adhesiveness, dyeability, metal adsorption ability, heavy metal carrying ability, and organic solvent affinity can be exhibited. In addition, by using a copolymer having such various amines, excellent plating adhesion to a molded body can be exhibited. When used for plating, etc., it is particularly preferable to use a monomer having a tertiary amine.

Specific examples of the monomer (B) include any monomer having a secondary or tertiary amine and selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene. This monomer exhibits hydrophilicity, ion conductivity, adhesion, dyeability, metal adsorption ability, heavy metal carrying ability, organic solvent affinity, etc., with the amine forming the side chain of the copolymer. Furthermore, any monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene forms the main chain of the copolymer.

In particular, to achieve these functions, it is preferable to use a monomer having a secondary, tertiary, or quaternary amine in the side chain of monomer (B). More specifically, secondary and tertiary amines are substituents having a structure represented by "-N(R1)(R2)", where R1 and R2 are each independently H or a hydrocarbon. The number of carbon atoms in this hydrocarbon can be, for example, 1 to 4.

The structure derived from monomer (B) is a structure of a side-chain crystalline block copolymer as block (B). The structural unit (B) derived from monomer (B) may have an amino group in the side chain, and thus may have an amine structure in the side chain. For example, the structural unit (B) may have a substituent represented by general formula (Y) in the side chain. In addition, general formula (Y) may be directly bonded to the main chain, or may be bonded to the main chain via a linking group such as an ester bond, an amide bond, an ether bond, a benzene ring, or an alkylene chain (alkylene group). The alkylene chain may have about 1 to 5 carbon atoms or about 1 to 3 carbon atoms.

In general formula (Y), R ^y1 and R ^y2 each independently represent a hydrogen atom, an alkyl group, or a carboxyalkylene group. Note that the carboxyalkylene group is a substituent in which a carboxy group and an alkylene group are bonded, and when the alkylene group is represented by R ^alkylene , it is a substituent represented by -R ^alkylene -COOH.
Among these, R ^y1 and R ^y2 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a carboxyalkylene group having 1 to 5 carbon atoms. The number of carbon atoms in the alkyl group or carboxyalkylene group may be 1 to 4. If the number of carbon atoms in the alkyl group or alkylene group represented by R ^y1 and R ^y2 is large, it may be difficult to interact with a metal.

In addition, these substituents may be bonded to any of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene via an alkylene chain having about 1 to 5 carbon atoms or about 1 to 3 carbon atoms, as appropriate. Examples include 2-(dimethylamino)ethyl methacrylate (DMAEMA), 2-(dimethylamino)ethyl acrylate (DMAEA), 2-(diethylamino)ethyl methacrylate (DEAEMA), 2-(diethylamino)ethyl acrylate (DEAEA), and 2-(tert-butylamino)ethyl methacrylate (TBAEMA).

[Amide group]
The monomer (B) may have an amide group. A monomer in which the amide group is bonded to the main chain structure via an alkylene chain having 1 to 5 carbon atoms or 1 to 3 carbon atoms, or directly, can be used. A copolymer using this monomer can impart hydrophilicity, ion conductivity, adhesiveness, dyeability, metal adsorption ability, heavy metal support, organic solvent affinity, and the like to a thermoplastic resin molded body. Specific examples of monomers having an amide group in a side chain include N,N-dimethylacrylamide (DMAA), N,N-dimethylaminopropyl acrylamide (DMAPAA), and N,N-diethylacrylamide (DEAA).

[Sulfo group]
The monomer (B) may have a sulfo group. In addition, a monomer in which the sulfo group is appropriately bonded to the main chain structure via an alkylene chain having about 1 to 5 carbon atoms or 1 to 3 carbon atoms, or directly, can be used. A copolymer using this monomer can impart hydrophilicity, proton conductivity, ion conductivity, adhesiveness, dyeability, metal adsorption ability, heavy metal supportability, organic solvent affinity, and the like to a thermoplastic resin molded body. Examples of monomers having a sulfo group include vinyl sulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, ATBS (Acrylamide Tertiary Butyl Sulfonic Acid), and its sodium salt ATBSNa.

[Oxyalkylene group]
The monomer (B) may have an oxyalkylene group. Here, the oxyalkylene group is a group represented by the general formula (-C _n H _2n O-). In this general formula, n is preferably an integer from 1 to 10. For example, when n is 1, it is called oxymethylene (-CH ₂ O-), and when n is 2, it is called oxyethylene (-CH ₂ CH ₂ O-). When a plurality of these oxyalkylene groups are linked together, it is called a polyoxyalkylene group (general formula: (-C _n H _2n O) _m -). A representative linear polyoxyalkylene group ((-(CH ₂ ) _n O) _m -) is polyoxyethylene ((-CH ₂ CH ₂ O) _m -), etc. may be mentioned. By preparing a copolymer using, as the monomer (B), a monomer having such an oxyalkylene group or polyoxyalkylene group as the main chain or side chain, it is possible to impart hydrophilicity, ion conductivity for Li or the like, adhesiveness, dyeability, metal adsorption ability, heavy metal supportability, organic solvent affinity, and the like to a molded article of a thermoplastic resin.

The monomer (B) having an oxyalkylene group may be any monomer selected from the group consisting of (meth)acrylates, (meth)acrylamides, vinyl ethers, vinyl esters, siloxanes, α-olefins, and substituted styrenes, each of which has an oxyalkylene group on its side chain. A copolymer using this monomer can impart hydrophilicity, ion conductivity, adhesiveness, dyeability, metal adsorption ability, heavy metal support, organic solvent affinity, and the like to a thermoplastic resin molded body. In addition, the use of such a copolymer can provide excellent plating adhesion to the resin molded body.

The structural unit (B) having an oxyalkylene group on the side chain can be, for example, one having a substituent represented by general formula (X) on the side chain. In addition, general formula (X) may be directly bonded to the main chain, or may be bonded to the main chain via a linking group such as an ester bond, an amide bond, an ether bond, a benzene ring, or an alkylene chain.

In formula (X), R ^x1 is a hydrogen atom or an alkyl group, p is an integer of 1 or more, and q is an integer of 1 or more.
The alkyl group represented by R ^x1 may be linear or branched, but is preferably linear. In addition, if the number of carbon atoms in the alkyl group is large, the interaction with the molded body of the thermoplastic resin becomes strong, and the metal adsorption ability may not be fully exhibited, or the interaction with the metal catalyst may become difficult. Therefore, R ^x1 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

p is preferably 1 to 10. Also, q is preferably 2 to 10, since it facilitates interaction with metals due to the chelating effect.

Examples of monomers having an oxyalkylene group include di(ethylene glycol) ethyl ether acrylate ( _CH2 =CH(CO)O( _CH2 - _CH2- O-) _2C2H5 ), polyethylene glycol monoacrylate ( _CH2 =CH(CO)O(CH2 _{- CH2 - O-} ) _nH ) (n=2-10), and methoxy-polyethylene glycol acrylate ( _CH2 =CH(CO)O( _CH2 - _CH2 -O-) _nCH3 ) (n= _2-9 ). Other examples include monomers having a polyoxyalkylene structure in the side chain, such as poly(ethylene glycol) monoacrylate (PGMA).

[Oxiranyl group]
The monomer (B) may be any monomer selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene having an oxiranyl group. Examples of the monomer (B) include glycidyl acrylate and glycidyl methacrylate.

The copolymer obtained using these monomers has an oxiranyl group in the side chain. When this oxiranyl group in the side chain is reacted with a compound having a tertiary amine such as iminodiacetic acid as a reactive group, the copolymer has a tertiary amine structure derived from iminodiacetic acid in the side chain, and exhibits metal adsorption ability.

[Chelate structure]
The structural unit (B) may have a chelate structure in the side chain. The chelate structure may be an iminodiacetic acid (IDA) group, a low molecular weight polyamino group, an aminophosphate group, an isothionium group, a dithiocarbamic acid group, a glucamine group, an oxyalkylene structure, or any other structure.

[General formulas (B-1) to (B-4)]
Specifically, the block (B) may have structures represented by the following general formulas (B-1) to (B-4), which are (meth)acrylate, (meth)acrylamide, and vinyl ether, respectively. , a structure having a vinyl ester.

In the general formulae (B-1) to (B-4), R ^b1 represents a hydrogen atom or a methyl group. R ^L represents a single bond or an alkylene chain, and is preferably a single bond or an alkylene chain having 1 to 4 carbon atoms. The alkylene chain may have a substituent such as an alkoxy group, a hydroxy group, or a hydroxyalkyl group, but an unsubstituted alkylene chain is preferred because this increases the degree of freedom of R ^b2 and makes it easier for the alkylene chain to assume a configuration that easily interacts with metals, thereby improving the affinity with metals.

In the general formulae (B-1) to (B-4), R ^b2 represents any one selected from the group consisting of a hydrogen atom, an alkylene chain, a hydroxy group, an amino group, a sulfo group, an oxiranyl group, and a substituent represented by the general formula (X). The substituent represented by the general formula (X) is as described above.
R ^b2 is preferably an amino group or a substituent represented by general formula (X) because it easily interacts with metals and provides better adhesion to the plating layer. The amino group may be an unsubstituted amino group (-NH ₂ ) or an amino group substituted with an alkyl group or the like, but the structure represented by general formula (Y) above is more preferred.

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

[General formulas (B-5) to (B-7)]
The block (B) may have structures represented by the following general formulas (B-5) to (B-7), which are structures having siloxane, α-olefin, and substituted styrene, respectively.

In the general formulae (B-5) to (B-7), R ^b1 represents a hydrogen atom or a methyl group. R ^L represents a single bond or an alkylene chain, and is preferably a single bond or an alkylene chain having 1 to 4 carbon atoms. The alkylene chain may have a substituent such as an alkoxy group, a hydroxy group, or a hydroxyalkyl group, but is preferably an unsubstituted alkylene chain.

R ^b4 represents any one selected from the group consisting of a hydroxy group, an amino group, a sulfo group, an oxiranyl group, and a substituent represented by general formula (X). The substituent represented by general formula (X) is as described above.

For example, when used in plating, R ^b4 is preferably an amino group or a substituent represented by general formula (X) because it easily interacts with metals and provides better adhesion to plating. The amino group may be an unsubstituted amino group (-NH ₂ ) or an amino group substituted with an alkyl group or the like, but the structure represented by general formula (Y) above is more preferred.

In the general formulas (B-1) to (B-7), m is an integer of 2 or more. m is appropriately determined depending on the structure of the group having metal adsorption ability, the arrangement of the structural unit (A) and the structural unit (B), the degree of polymerization of the structural unit (B), etc.

In the side chain crystalline block copolymer, m is preferably 2 to 1,000. In order to exert a more stable modifying effect and impart metal adsorption ability to the surface of a molded thermoplastic resin body, m is preferably 2 or more, and more preferably 5 or more or 10 or more. Furthermore, m may be 800 or less, or 500 or less, as long as the effects of the structural unit (A) and the structural unit (B) are sufficiently obtained.

[Copolymer]
The side chain crystalline block copolymer is a copolymer containing a structural unit (A) and a structural unit (B). The side chain crystalline block copolymer may further contain other structural units within a range that does not impair the object of the present invention. For example, as described below, when the structural unit (B) is obtained by introducing a metal-adsorbing site into the side chain of its precursor polymer, the side chain crystalline block copolymer may contain a structure derived from the precursor monomer of the structural unit (B) in addition to the copolymer (A) and the copolymer (B).

The side-chain crystalline block copolymer contains the structural unit (A) and the structural unit (B) as main components, and the total proportion of the structural unit (A) and the structural unit (B) in the side-chain crystalline block copolymer is preferably 80% by mass or more, and more preferably 90% by mass or more.

One preferred side chain crystalline block copolymer is a copolymer containing a block (A) represented by general formula (A-1) or (A-2) and a block (B) represented by general formula (B-1), and more preferably a copolymer containing a block (A) represented by general formula (A-1) and a block (B) represented by general formula (B-1).

The side chain crystalline block copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a triblock copolymer, etc., but is preferably a block copolymer. By using a block copolymer, the respective functions of the structural unit consisting of block (A) and the structural unit consisting of block (B) can be easily and sufficiently exerted.

In the side-chain crystalline block copolymer, the molecular weight corresponding to block (A) and the molecular weight corresponding to block (B) are each preferably 1000 or more. When the molecular weight corresponding to block (A) is 1000 or more, it can adhere more firmly to the molded body of thermoplastic resin that serves as the substrate. The molecular weight corresponding to block (A) is preferably 1,500 or more, and more preferably 2,000 or more.

In addition, by having a molecular weight corresponding to block (B) of 1000 or more, a copolymer with superior metal adsorption ability can be obtained. The molecular weight corresponding to block (B) is preferably 1,500 or more, and more preferably 2,000 or more.

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

An example of a side-chain crystalline block copolymer is the polymer represented by the following chemical formula (I). This is a block copolymer obtained by polymerizing behenyl acrylate (BHA: the side chain is a linear alkyl group having 22 carbon atoms) as the monomer (A) and then copolymerizing it with 2-(tert-butylamino)ethyl methacrylate (TBAEMA) as the monomer (B). This is a so-called AB-type block copolymer. This copolymer has a block copolymer portion that exhibits adhesion to thermoplastic resin molded bodies due to the structure derived from BHA, while the amine structure derived from TBAEMA can impart metal adsorption ability to thermoplastic resin molded bodies (workpieces).

Other examples of side-chain crystalline block copolymers include polymers of chemical formulas (II), (III), and (IV). These use stearyl acrylate (STA) as monomer (A). Also, TBAEMA, diethylene glycol monoethyl ether acrylate (DEEA), and acrylic acid (AA) as monomer (B).

[Polymerization method]
The polymerization method of the side chain crystalline block copolymer is not particularly limited, and the copolymerization can be performed by known techniques such as various living polymerization methods (radical, anionic, cationic). As the living radical polymerization method, the NMP method, the ATRP method, the RAFT method, etc. can be used. In addition, as described above, the side chain crystalline block copolymer is preferably a block copolymer, and is preferably produced to be a block copolymer.

For example, it can be obtained by polymerizing a monomer (A) selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, which has an alkane chain with 8 or more carbon atoms in its side chain, with a monomer (B1) having a structure with metal adsorption ability in its side chain.

Specifically, a monomer (A) mixed solution preparation step is performed in which monomer (A) is mixed with an initiator in a polymerization solvent to prepare a monomer (A) mixed solution. Next, the monomer (A) mixed solution prepared in this mixed solution preparation step is subjected to a monomer (A) polymerization step based on the polymerization mechanism of the initiator, such as living radical polymerization, in a nitrogen atmosphere or the like, while appropriately stirring the monomer (A) mixed solution prepared in the mixed solution preparation step at an appropriate polymerization temperature (e.g., about 90 to 120°C), to obtain a monomer (A) block polymer.

Furthermore, a monomer (B1) having a structure with metal adsorption ability in the side chain (e.g., (meth)acrylate having an amino group) is mixed into the solution in which the monomer (A) block polymer is mixed, and a monomer (B1) polymerization step is carried out in which the monomer (B1) is further polymerized by radicals in the solution. This makes it possible to obtain a block copolymer having a block derived from monomer (A) and a block derived from monomer (B1). The order in which the monomer (A) and monomer (B1) are polymerized can be changed depending on the type of monomer to be polymerized, the weight average molecular weight, the polymerization conditions for each, etc.

[Use of precursor polymer]
Alternatively, the structural unit (B) can be obtained by polymerizing monomer (A) with monomer (B2) (a precursor monomer of structural unit (B)) having a reactive group such as an oxiranyl group on its side chain to synthesize a precursor polymer, and then reacting the precursor polymer with an amino group or the like.

Specifically, as described above, monomer (A) is mixed with an initiator in a polymerization solvent, and the monomer (A) polymerization step is carried out based on the polymerization mechanism of the initiator, such as living radical polymerization, in a reactor at an appropriate polymerization temperature (e.g., about 90 to 120°C) while being appropriately stirred, under a nitrogen atmosphere, etc., to obtain a monomer (A) block polymer.

A monomer (B2) having an oxiranyl group (e.g., a (meth)acrylate having an oxiranyl group) is mixed into the solution in which the monomer (A) block polymer is mixed, and a monomer (B2) polymerization step is carried out in which the monomer (B2) is further polymerized by radicals in the solution. This results in a solution in which a precursor polymer having a block derived from monomer (A) and a block derived from monomer (B2) is mixed. Next, when this precursor polymer is reacted with iminodiacetic acid, the oxiranyl group reacts with iminodiacetic acid to form an amine structure derived from iminodiacetic acid, and a copolymer having metal adsorption ability in the side chain of the block derived from monomer (B2).

When other structural units are included, they may be polymerized with monomer (A) and monomer (B) to form monomer (C).

The side-chain crystalline block copolymer thus synthesized can be used in a concentrated or dried state, such as in a paste or powder form, by heating or spray drying as appropriate.

The method for producing a molded body of the present invention involves melt-molding a kneaded resin into a molded body, thereby modifying the surface layer and the layer near the surface of the molded body.

[Mixed resin]
The kneaded resin containing the thermoplastic resin and the side chain crystalline block copolymer can be prepared by any method. The kneaded resin may be prepared by kneading the thermoplastic resin and the side chain crystalline block copolymer in advance in a melt kneader to form a mass, which is then crushed appropriately to obtain a master batch.

The master batch may have a higher concentration of the side chain crystalline block copolymer than that in the modified molded body, making it easier to handle the side chain crystalline block copolymer. For example, the concentration of the side chain crystalline block copolymer in the master batch resin may be 5 to 80 mass%, 10 to 80 mass%, 30 to 80 mass%, or 40 to 80 mass%, etc. Such a master batch and a thermoplastic resin may be mixed in a dry state to control the concentration of the side chain crystalline block copolymer when producing the molded body of the present invention.

The components may also be mixed in a dry state so as to be dispersed, and then fed into the hopper of the molding machine as a raw material to be kneaded into a resin in the melt-kneading section of the molding machine. The premix may also be kneaded in a pelletizer or the like to form pellets, and the pellets may be used as raw material for further molding.

[ratio]
The content of the side-chain crystalline block copolymer in the kneaded resin (mass of side-chain crystalline block copolymer/mass of kneaded resin) is preferably 0.05 to 10.0 mass %. By setting the content within this range, a molded article having a surface layer modified by the side-chain crystalline block copolymer can be efficiently obtained.

If the content of the side chain crystalline block copolymer in the kneaded resin exceeds 10.0% by mass, the surface modification effect of the molded article may become saturated. In addition, since there is a large amount of side chain crystalline block copolymer, self-aggregation into micelles may occur, and the side chain crystalline block copolymer may form lumps in the inner layer or may appear in a spotty form on the surface. The content of the side chain crystalline block copolymer in the kneaded resin is more preferably 7.0% by mass or less, and may be 6.0% by mass or less, 5.0% by mass or less, 4.0% by mass or less, 3.5% by mass or less, or 3.0% by mass or less.

If the content of the side chain crystalline block copolymer is less than 0.05% by mass, the modifying effect may not be obtained. This content is more preferably 0.08% by mass or more, and may be 0.10% by mass or more, 0.15% by mass or more, 0.2% by mass or more, or 0.3% by mass or more.

[Pellet molding machine 10]
Fig. 1 shows an example of a pellet molding machine for forming pellets, and Fig. 2 shows an example of a film molding machine for forming a film. These molding machines are suitable for the manufacturing method of the present invention.

The pellet molding machine 10 in FIG. 1 has a supply port 11, a supply port 12, a melt kneading section 2, a discharge section 3, and a pelletizer 4. This pellet molding machine 10 can melt a resin composition and mold it into pellets. The resulting pellets 61 are collected in a container 5 such as a flexible container bag. The pellet molding machine 10 will be described in more detail below.

[Supply ports 11, 12]
The supply ports 11 and 12 are hopper-shaped supply ports. A thermoplastic resin composition in the form of a lump, powder, pellets, or the like is supplied from the top of the supply ports 11 and 12 and transferred to the melt-kneading section 2. Different raw materials can be fed into the supply ports 11 and 12, respectively. For example, a thermoplastic resin can be fed into the supply port 11, and a side-chain crystalline block copolymer can be fed into the supply port 12.

[Melting and kneading section 2]
The melt-kneading section 2 melts and kneads the thermoplastic resin composition supplied from the supply ports 11 and 12. The melt-kneading section 2 is heated to the melting temperature of the thermoplastic resin composition, and the thermoplastic resin composition is extruded by rotating a screw 22 connected to a cylinder 21 by a motor M. In addition, when passing between the pipe and the screw, etc., a shear stress is applied to the thermoplastic resin composition, and the thermoplastic resin composition is kneaded.

[Discharge section 3]
The discharge section 3 discharges the thermoplastic resin composition after melt kneading in the form of strands. The pelletizer 4 chops the thermoplastic resin composition in the form of strands discharged from the discharge section 3 into pellets. The molding machine of the present invention may pelletize the composition by hot cutting or underwater cutting, which chops the composition immediately after discharge from the discharge section, and the strand shape also includes short strands. The molding machine of the present invention may be a molding machine having a chopping section that chops the thermoplastic resin composition discharged from such a discharge section into pellets.

The resin pellets obtained by pelletizing the thermoplastic resin composition using this pellet molding machine 10 can be used as masterbatches, which can also be used as raw materials when manufacturing molded products.

[Molding temperature]
The molding temperature of the molded article of the present invention may be a standard molding temperature for the thermoplastic resin that is the main component, and this temperature can be controlled by the setting temperature of the screw part of the injection molding machine, etc.

In the molding machine 101 of FIG. 2, instead of the pelletizer 4 of the molding machine 10 of FIG. 1, a T-die 51 for film formation is attached after the discharge section 3. Also, instead of the supply ports 11 and 12, only the supply port 1 is provided. The resin composition discharged from the T-die 51 is discharged onto a roller 52, and formed into a film 62 while being appropriately stretched by a stretching roller (not shown) or the like, and then wound up on a winding roller 53.

[Molded body]
The molded article of the present invention contains a thermoplastic resin and a side-chain crystalline block copolymer. The shape of the molded article molded using these resin compositions is not particularly limited, and examples thereof include molded articles such as sheets, plates, threads, filaments, fibers, porous materials, various members, and structures.

The molded article of the present invention has an orientation layer in which the side-chain crystalline block copolymer is selectively distributed and arranged in the surface layer, and a dispersion layer containing the side-chain crystalline block copolymer in the surface vicinity layer in contact with the orientation layer. The side-chain crystalline block copolymer in the surface layer and the surface vicinity layer may be confirmed by identifying the presence or absence and the degree of the side-chain crystalline block copolymer in each part in the thickness direction by IR. Alternatively, when the surface is washed, it may be confirmed by maintaining a certain degree of the physical properties modified by the presence of the surface vicinity layer. The surface layer is a layer directly exposed to the outside of the molded article. The surface vicinity layer is a layer inside this surface layer and close to the surface layer.

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

[Evaluation items]
[IR spectrum]
The measurement was carried out using a Fourier transform infrared spectrometer "Spectrum two (registered trademark)" manufactured by Perkin Elmer.

[Tensile shear test (adhesion)]
A tensile shear test was carried out in accordance with JIS K6850 (1999) to evaluate the adhesiveness. A cyanoacrylate adhesive (product name: Aron Alpha 201, manufactured by Toagosei Co., Ltd.) was used as the adhesive. A small tabletop tester EZ-LX manufactured by Shimadzu was used as the test device. The test piece was 25 mm wide and 100 mm long, with an adhesive length of 12.5 mm.
Both ends of the test piece were held by grippers of the measuring device and pulled apart at 10 mm/min to measure the adhesive strength.
The test was carried out three times, and the average value of the maximum load over the entire measurement range was calculated (represented as "maximum load (breaking force N)" in the table).

[Raw materials]
HDPE: Asahi Kasei Corporation "Suntech (registered trademark) F184"
・LDPE: UBE Maruzen Polyethylene Co., Ltd. "UBE Polyethylene F522N"
・L-LDPE: Asahi Kasei Corporation "Yumerit (registered trademark) 3540N"
PP: Prime Polypro (registered trademark) J137G, Prime Polymer Co., Ltd.
Block PP: Prime Polypro (registered trademark) B-150, Prime Polymer Co., Ltd.

[Monomer (A)]
Monomer (A-1-1): BHA behenyl acrylate was used. This monomer has an alkyl group with 22 carbon atoms in the side chain.

[Monomer (B)]
Monomer (B-1-1): TBAEMA 2-(tert-butylamino)ethyl methacrylate (TBAEMA) was used. This monomer has a secondary amino group in the side chain and a methacrylate structure as the main chain.

[Polymerization initiator] BlocBuilder (registered trademark) MA (manufactured by Arkema)
[Solvent] Butyl acetate

[1] Production of block copolymer (1-1) Production of block copolymer (BHA-TBAEMA) 5.0 parts by mass of butyl acetate and 5.0 parts by mass of behenyl acrylate (BHA) were placed in a separable flask, and the butyl acetate and BHA were mixed, followed by degassing and nitrogen replacement. Under a nitrogen atmosphere, the mixture of butyl acetate and BHA was stirred to dissolve BHA in butyl acetate, and then 0.38 parts by mass of an initiator (Blocbuilder MA) was added. Under a nitrogen atmosphere, BHA was polymerized at 110°C for 24 hours to obtain a solution of BHA polymer.
To the BHA polymer solution, 5.0 parts by mass of 2-(tert-butylamino)ethyl methacrylate (TBAEMA) and 5.0 parts by mass of butyl acetate were added, and polymerization was further carried out for 24 hours at 110° C. under a nitrogen atmosphere. Methanol was added to cause reprecipitation and drying, thereby obtaining a block copolymer of BHA and TBAEMA (BHA-TBAEMA).

The structural formula of the obtained BHA-TBAEMA is shown below as general formula (I). The block copolymer (BHA-TBAEMA) obtained in (1-1) had an Mw of 10,000.

[Kneading conditions]
The thermoplastic resin and the side chain crystalline block copolymer were weighed and mixed in a dry state.
Mixer: A "Labo Plastomill 4C150" manufactured by Toyo Seiki Seisakusho was used to carry out preliminary mixing to prepare a master batch.
PE (HDPE, LDPE, L-LDPE) was kneaded at 180° C., 30 rpm, and 3 minutes.
PP (block PP) was kneaded at 210° C., 30 rpm, and 3 minutes.

[Polyethylene (PE) film formation conditions]
Film-forming conditions (A): The bulk kneaded composition obtained by preliminary kneading was placed in a spacer having a thickness of 500 μm using a press molding machine, and press-molded at a press temperature of 180° C., a press pressure of 25 MPa, and a heating time of 2 minutes to obtain a film-shaped molded body.
Film-forming condition (B): From the film formed under the film-forming condition (A), the remainder after taking an adhesion test piece was recovered, and the kneaded composition was used to form a film in accordance with the film-forming condition (A).
Film-forming conditions (C): A thermoplastic resin and a side-chain crystalline block copolymer were weighed out and mixed in a dry state. The mixture was placed in a spacer having a thickness of 500 μm using a press molding machine and press-molded at 180° C. to melt-knead and mold the mixture in the spacer of the press molding machine, thereby obtaining a film-like molded product.

[Polyethylene (PP) film formation conditions]
A film was formed under the same conditions as those for forming the polyethylene film, except that the press temperature was changed from 180° C. to 210° C.

Tables 1 to 3 show the conditions and evaluation results of test examples in which film-making conditions were changed, such as the type and concentration of thermoplastic resin and side-chain crystalline block copolymer (SCCBC).

[Test Examples A1 to A14 and Comparative Example 1 (Table 1)]
Table 1 relates to tests using HDPE. When HDPE was used, an improvement in adhesive strength was observed at 0.1 wt% or more in re-pressing (film-forming condition (B)) and kneading (film-forming condition (A)). On the other hand, a decrease in adhesive strength was observed at 5 wt% or more. At 5 wt%, adhesive strength improved by re-pressing, but at 10 wt%, the adhesive strength improvement effect was low even after re-pressing.

[Test Examples B1 to B14 (Table 2)]
Table 2 shows the results of the test using PP. When PP was used, the adhesive strength was improved when the SCCBC was 1.0 wt% or more. On the other hand, when the SCCBC was 10 wt% or more, the adhesive strength started to decrease.

[Test Examples C1 to C6 (Table 3)]
The evaluation results using various thermoplastic resins are shown in Table 3. LDPE, L-LDPE, and block PP all had such strong adhesiveness that the substrate stretched or broke before peeling occurred at the adhesive surface.

The molded articles of the thermoplastic resin composition obtained by the present invention can be used in various applications as products with improved physical properties of conventional thermoplastic resin compositions, and are industrially useful.

Reference Signs List 1, 11, 12 Supply port 10, 101 Molding machine 2 Melt kneading section 21 Cylinder 22 Screw 3 Discharge section 4 Pelletizer 5 Container 51 T-die 52 Roller 53 Winding roller 61 Pellet 62 Film

Claims (3)

The method for producing a molded article includes melt molding a kneaded resin obtained by kneading a thermoplastic resin and a side-chain crystalline block copolymer, and modifying a surface layer of the molded article,
the side chain crystalline block copolymer comprises a first polymer block which is a repeat of a structural unit having an alkyl group having 8 or more carbon atoms in a side chain, and a second polymer block which is a repeat of a structural unit having a functional group;
the first polymer block is a polymer of any one monomer (A) selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, the monomer having an alkyl group having 8 or more carbon atoms;
the second block is a polymer of any one of monomers (B) selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, the monomer (B) having any one of groups selected from the group consisting of an amino group, an amide group, a sulfo group, an oxyalkylene group, and an oxiranyl group,
the thermoplastic resin is one or more resins selected from the group consisting of polyolefin-based resins, polyester-based resins, polystyrene-based resins, and polyacrylic-based resins;
The method for producing a molded article, wherein the content of the side-chain crystalline block copolymer in the kneaded resin (mass of side-chain crystalline block copolymer/mass of kneaded resin) is 0.05 to 10.0 mass % . The method for producing a molded article according to claim 1 , wherein the functional group is a polar group and/or a functional group having a metal adsorption ability. The composition contains a thermoplastic resin and a side-chain crystalline block copolymer,
a surface layer having a portion where the side chain crystalline block copolymer is selectively distributed and arranged;
a surface vicinity layer in contact with the surface layer and having a portion containing the side chain crystalline block copolymer ,
the side chain crystalline block copolymer comprises a first polymer block which is a repeat of a structural unit having an alkyl group having 8 or more carbon atoms in a side chain, and a second polymer block which is a repeat of a structural unit having a functional group;
the first polymer block is a polymer of any one monomer (A) selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, the monomer having an alkyl group having 8 or more carbon atoms;
the second block is a polymer of any one of monomers (B) selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl ester, siloxane, α-olefin, and substituted styrene, the monomer (B) having any one of groups selected from the group consisting of an amino group, an amide group, a sulfo group, an oxyalkylene group, and an oxiranyl group,
the thermoplastic resin is one or more resins selected from the group consisting of polyolefin-based resins, polyester-based resins, polystyrene-based resins, and polyacrylic-based resins;
The content of the side chain crystalline block copolymer is 0.05 to 10.0% by mass.