Resin composition for 3D printer, and molding of the same

Abstract

To provide a resin composition for a 3D printer using a copolymer or an ionomer excellent in moldability hard to generate shrinkage, and sag, and good in impact resistance and flexibility.SOLUTION: A resin composition for a 3D printer includes: an ionomer having a neutralization amount of 0.4 to 10 mol% in which at least a part of a carboxyl group and / or a dicarboxylic acid anhydride group is converted into a metal-containing carboxylic acid salt containing at least one metal ion in a copolymer (P) including a structural unit (A) derived from ethylene and / or a 3-20C α-olefin, and a structural unit (B) derived from a monomer having a carboxyl group and / or a monomer having a dicarboxylic acid anhydride group as essential constituent units; and a thermoplastic resin optionally other than those falling under the ionomer, where an amount of the ionomer is 50 mass% or more to a total resin composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition for a 3D printer and a molded article thereof.

Background Art

[0002] 3D printing is a technology for manufacturing three-dimensional objects based on three-dimensional model data created by a computer. Different from molding with a mold or shaping by cutting, 3D printing technology does not require a mold or cutting tool, can immediately respond to frequent design changes, and can create hollow shapes or complex internal shapes. Therefore, 3D printing technology is a technology that is rapidly spreading in a wide range of fields.

[0003] In 3D printing, it is common for shaping to be performed by laminating the cross-sectional shapes of three-dimensional model data, and it is collectively called Additive manufacturing, including various lamination methods. Among various lamination methods, the method called the material extrusion method is easy to use because it does not require additional equipment. The material extrusion method is a method of shaping a three-dimensional shape by melting a thermoplastic resin processed into a pellet or filament state and laminating it while extruding it. Plastics such as PLA and ABS resins can also be used, and molded articles can be shaped according to the characteristics of each plastic. Since the operability of shaping with a 3D printer changes depending on the physical properties of the resin, various resins have been tried as resins for 3D printers (Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] Although 3D printing technology using the material extrusion method has many advantages, it may be difficult to use depending on the physical properties of the resin. For example, unlike cutting into fixed dimensions, 3D printing using the material extrusion method has a process of cooling the molten resin after extrusion. Therefore, if there are dimensional changes such as warping during cooling, it may not be possible to form the desired shape. In addition, the formability to be able to form exactly as designed down to the details is also important. For good formability, it is important not only that the molded product is difficult to warp, but also that it is difficult for sagging to occur. Sagging refers to the fact that when forming fine parts, the time until the next layer is laminated is short, and molten resin is laminated on a layer where the resin is not sufficiently hardened, and the shape cannot be maintained due to its own weight, resulting in poor forming. Furthermore, fluidity is also important as a physical property of the resin that affects formability. If the fluidity of the resin is poor, discharge defects such as resin clogging in the nozzle may occur, making it difficult to form. On the other hand, molded products formed by a 3D printer need to be designed with consideration for safety during handling while having sufficient mechanical properties. The characteristics required for these molded products in terms of safety are greatly influenced not only by the shape of the molded product but also by the properties of the resin for 3D printers. From the viewpoint of warpage prevention, amorphous or thermoplastic resins with a slow crystallization rate are mainly selected in the material extrusion method. On the other hand, although polyolefin has the advantages of being inexpensive and having excellent mechanical properties, it has been considered unsuitable for 3D printing because it is a crystalline resin and shrinkage occurs. PLA resin, which is widely used as a 3D printing material, is known for its low shrinkage and high shaping accuracy. However, it has high rigidity and low impact resistance, making the molded product prone to breakage. Moreover, the broken cross-section becomes sharp, increasing the risk of injury. On the other hand, ABS resin has excellent impact resistance but high rigidity, large warpage during 3D printing, and poor dimensional stability. Thus, plastics used for 3D printers are required to have excellent shaping properties such as low warpage and sagging during cooling, and characteristics excellent in impact resistance and flexibility from the perspective of safety. The present application aims to provide such a resin for 3D printers.

Means for Solving the Problems

[0006] The inventors have found that the above problems can be solved by using an ionomer having specific characteristics. An ionomer is an ionic polymer having a pseudo-crosslinked structure by having a carboxyl group and a metal ion. The inventors have discovered that the ionic crosslinking, which is a characteristic of the ionomer, can reduce the crystallinity and suppress the occurrence of shrinkage, and can also prevent sagging by imparting the characteristic of significantly changing the viscosity with a small temperature change. From the above situation, it has been found that the ionomer in the present invention can exhibit excellent shaping properties by suppressing the occurrence of warpage, sagging, nozzle clogging, etc. of the molded product. Furthermore, it has been found that a flexible molded product with good impact resistance and consideration for safety can be shaped, leading to the creation of the present invention. That is, the present invention relates to the following items. [1] A 3D printer resin composition comprising an ionomer in which at least a part of carboxyl groups and / or dicarboxylic anhydride groups in a copolymer (P) containing a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group as essential constituent units is converted into a metal-containing carboxylate containing at least one kind of metal ion, and the neutralization amount is 0.4 to 10 mol%, and optionally a thermoplastic resin not corresponding to the ionomer, wherein the amount of the ionomer is 50% by mass or more based on the whole resin composition. [2] The 3D printer resin composition according to [1] above, wherein the copolymer (P) contains 1.0 to 20.0 mol% of the structural unit (B) in the copolymer. [3] The 3D printer resin composition according to [1] or [2] above, comprising an ionomer in which at least a part of carboxyl groups and / or dicarboxylic anhydride groups of the copolymer (P) is neutralized to 1% to 90% with a metal-containing carboxylate containing at least one kind of metal ion. [4] The 3D printer resin composition according to any one of [1] to [3] above, wherein the structural unit (A) is a structural unit derived from ethylene. [5] The 3D printer resin composition according to any one of [1] to [4] above, wherein the metal ion is at least one kind of metal ion selected from Group 1, Group 2 or Group 12 of the periodic table. [6] The 3D printer resin composition according to any one of [1] to [5] above, wherein the activation energy of flow of the ionomer is 40 kJ / mol or more. [7] The 3D printer resin composition according to any one of [1] to [6] above, wherein the crystallinity of the ionomer is 50% or less. [8] The 3D printer resin composition according to any one of [1] to [7] above, wherein the melting point of the ionomer is in the range of 60°C to 130°C. [9]A 3D printed molded article, wherein the resin composition for a 3D printer according to any one of [1] to [8] above is molded by deposition of one or more lines by deposition of the molten resin.

[10] A method for manufacturing a 3D printed molded article, comprising a step of depositing the resin composition for a 3D printer according to any one of [1] to [8] above in a plurality of layers using a 3D printer to form a molded article.

Effects of the Invention

[0007] According to the present invention, by using an ionomer having specific characteristics, there are provided a resin composition for a 3D printer and a molded article using the same, which are excellent in moldability, impact resistance, flexibility, etc.

Modes for Carrying Out the Invention

[0008] The present invention includes a copolymer (P) containing structural units (A) derived from ethylene and / or α-olefins having 3 to 20 carbon atoms and structural units (B) derived from monomers having a carboxyl group and / or a dicarboxylic anhydride group as essential constituent units, and at least a part of the carboxyl group and / or the dicarboxylic anhydride group in the copolymer (P) is converted into a metal-containing carboxylate containing one kind of metal ion, and an ionomer having a neutralization amount of 0.4 to 10 mol%, and optionally a thermoplastic resin not corresponding to the ionomer, and the amount of the ionomer is 50% by mass or more based on the whole resin composition, and a resin composition for a 3D printer and a molded article using the resin.

[0009] Hereinafter, the resin composition of the present invention and the ionomer related thereto will be described in detail item by item. In the present application, “(meth)acrylic acid” means acrylic acid or methacrylic acid. In the present application, “~” indicating a numerical range is used in the sense of including the numerical values described before and after as a lower limit value and an upper limit value. In the present application, the copolymer (P) means a binary or higher copolymer containing at least one kind of structural unit (A) and at least one kind of structural unit (B). In the present application, the ionomer means a binary or higher copolymer ionomer containing the structural unit (A) and the structural unit (B’) in which at least a part of the structural unit (B) is converted by a metal-containing carboxylate, and may further contain the structural unit (B).

[0010] <Ionomer> The ionomer of the present invention contains, as essential constituent units, a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group. A copolymer (P) in which these are randomly copolymerized is used as a base resin, and at least a part of the carboxyl group and / or the dicarboxylic anhydride group of the structural unit (B) is converted into a metal-containing carboxylate containing at least one kind of metal ion.

[0011] (1) Structural unit (A) The structural unit (A) is at least one structural unit selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms. The α-olefin related to the present invention has the structural formula: CH 2 =CHR 18 and is an α-olefin having 3 to 20 carbon atoms (R 18 is a hydrocarbon group having 1 to 18 carbon atoms and may have a linear structure or a branch). The carbon number of the α-olefin is more preferably 3 to 12.

[0012] Specific examples of the structural unit (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene, etc., and ethylene may be used. As ethylene, in addition to those derived from petroleum raw materials, ethylene derived from non-petroleum raw materials such as plant raw materials can be used. Also, the structural unit (A) may be of one kind or a plurality of kinds. Examples of the two-component combinations include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. Examples of the three-component combinations include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene.

[0013] The structural unit (A) of the present invention preferably contains ethylene as an essential component, and may further contain one or more α-olefins having 3 to 20 carbon atoms as necessary. Ethylene in the structural unit (A) may be 50 to 100 mol%, 70 to 100 mol%, or 90 to 100 mol% based on the total moles of the structural unit (A).

[0014] (2) Structural unit (B) The structural unit (B) is a structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group. Note that the structural unit (B) represents the same structure as the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and as described in the manufacturing method described later, it does not necessarily have to be produced using a monomer having a carboxyl group and / or a dicarboxylic anhydride group.

[0015] Examples of the structural unit derived from a monomer having a carboxyl group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid, bicyclo[2,2,1]hepta-2-ene-5,6-dicarboxylic acid, etc. Examples of the structural unit derived from a monomer having a dicarboxylic anhydride group include unsaturated dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, tetracyclo[6.2.1.1 3,6 .0 2,7 dodeca-9-ene-4,5-dicarboxylic anhydride, 2,7-octadien-1-ylsuccinic anhydride, etc. As the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, from the viewpoint of easy industrial availability, preferably, a structural unit derived from acrylic acid, methacrylic acid, or 5-norbornene-2,3-dicarboxylic anhydride may be mentioned, and particularly, a structural unit derived from acrylic acid may also be mentioned. In addition, the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group may be of one kind or a plurality of kinds.

[0016] Note that the dicarboxylic anhydride group may react with moisture in the air to open the ring and partially become a dicarboxylic acid. However, as long as it does not deviate from the gist of the present invention, the dicarboxylic anhydride group may be in an open-ring state.

[0017] (3) Other structural units (C) The copolymer (P) related to the present invention may contain a structural unit (A) and a structural unit (C) other than the structural unit (B). As the monomer that provides the structural unit (C), any monomer can be used as long as it is not included in the monomers that provide the structural unit (A) and the structural unit (B). The monomer that provides the structural unit (C) is not limited as long as it is a compound having one or more carbon-carbon double bonds in its molecular structure. Examples thereof include an acyclic monomer represented by the following general formula (1) and a cyclic monomer represented by the following general formula (2).

[0018] ·Acyclic monomer [Chemical formula] [In general formula (1), T 1 ~T 3 are each independently a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group, T 4 is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group.]

[0019] T 1 ~T 4The hydrocarbon group, substituted alkoxy group, substituted ester group, alkoxy group, aryl group, ester group, and silyl group may have a branched structure, a ring structure, and / or an unsaturated bond. T 1 ~T 4 The number of carbon atoms in the hydrocarbon group may be 1 or more as the lower limit and 20 or less as the upper limit, and may be 10 or less. T 1 ~T 4 The number of carbon atoms in the substituted alkoxy group may be 1 or more as the lower limit and 20 or less as the upper limit, and may be 10 or less. T 1 ~T 4 The number of carbon atoms in the substituted ester group may be 2 or more as the lower limit and 20 or less as the upper limit, and may be 10 or less. T 1 ~T 4 The number of carbon atoms in the alkoxy group may be 1 or more as the lower limit and 20 or less as the upper limit, and may be 10 or less. T 1 ~T 4 The number of carbon atoms in the aryl group may be 6 or more as the lower limit and 20 or less as the upper limit, and may be 11 or less. T 1 ~T 4 The number of carbon atoms in the ester group may be 2 or more as the lower limit and 20 or less as the upper limit, and may be 10 or less. T 1 ~T 4 The number of carbon atoms in the silyl group may be 3 or more as the lower limit and 18 or less as the upper limit, and may be 12 or less. Examples of the silyl group include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, and triphenylsilyl group.

[0020] In the ionomer of the present invention, from the viewpoint of ease of production, T 1 and T 2 may be a hydrogen atom, and T 3may be a hydrogen atom or a methyl group, T 1 ~T 3 may all be hydrogen atoms, T 4 may be an ester group having 2 to 20 carbon atoms.

[0021] Specific examples of the acyclic monomer include (meth)acrylic acid esters and the like, where T 4 is an ester group having 2 to 20 carbon atoms. T 4 When T is an ester group having 2 to 20 carbon atoms, examples of the acyclic monomer include compounds represented by the structural formula: CH 2 =C(R 21 )CO 2 (R 22 ). Here, R 21 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may have a branch, a ring, and / or an unsaturated bond. R 22 is a hydrocarbon group having 1 to 20 carbon atoms, which may have a branch, a ring, and / or an unsaturated bond. Further, any position within R 22 may contain a hetero atom. Structural formula: CH 2 =C(R 21 )CO 2 (R 22 ). Examples of the compound represented by the structural formula include compounds where R 21 is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Also, examples include acrylic acid esters where R 21 is a hydrogen atom or methacrylic acid esters where R 21 is a methyl group. Structural formula: CH 2 =C(R 21 )CO 2 (R 22Specific examples of the compound represented by [formula] include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, and the like. Specific compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate (nBA), isobutyl acrylate (iBA), t-butyl acrylate (tBA), 2-ethylhexyl acrylate, and the like, and particularly n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA) may also be used. The acyclic monomer may be of one kind or a plurality of kinds.

[0022] · Cyclic monomer [Chemical formula] [In general formula (2), R 1 ~R 12 may be the same or different from each other, and is selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. R 9 and R 10 , and R 11 and R 12 may each integrally form a divalent organic group. R 9 or R 10 and R 11 or R 12 may form a ring with each other. Further, n represents 0 or a positive integer. When n is 2 or more, R 5 ~R 8Within each repeating unit, they may be the same or different from each other.

[0023] Examples of the cyclic monomer include norbornene-based olefins and the like, such as norbornene, vinyl norbornene, ethylidene norbornene, norbornadiene, tetracyclododecene, tricyclo[4.3.0.1 2,5 , tricyclo[4.3.0.1 2,5 deca-3-ene, and compounds having a cyclic olefin skeleton such as these, and 2-norbornene (NB), and tetracyclo[6.2.1.1 3,6 .0 2,7 dodeca-4-ene and the like may also be used.

[0024] (4) Metal ions The metal ions of the carboxylate group are not particularly limited, but preferably divalent metal ions selected from the group consisting of Group 1, Group 2, or Group 12 of the periodic table. Specifically, ions of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), and zinc (Zn) and the like may be mentioned. From the viewpoint of ease of handling, ions of sodium (Na), magnesium (Mg), calcium (Ca), or zinc (Zn) may also be used, and particularly, ions of sodium (Na), magnesium (Mg), or calcium (Ca) are more preferable. The carboxylate group can be obtained by, for example, hydrolyzing or thermally decomposing the ester group of the copolymer and then reacting it with a compound containing the above metal ions, or by reacting it with the compound containing the above metal ions while hydrolyzing or thermally decomposing, thereby converting the ester group portion in the copolymer into a metal-containing carboxylate. Note that the metal ions may be of one type or a plurality of types.

[0025] (5) Copolymer (P) The copolymer (P) serving as the ionomer-based resin used in the present invention comprises, as essential constituent units, a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and further optionally contains an arbitrary structural unit (C), and is characterized in that these respective structural units are copolymerized, preferably randomly copolymerized. More preferably, it is characterized in that they are copolymerized in a substantially linear form. "Substantially linear" means that the copolymer (P) has no branches or the frequency of the appearance of a branched structure is small, and it is a state in which the copolymer (P) can be regarded as linear. Specifically, it refers to a state in which the phase angle δ of the copolymer (P) is 50 degrees or more.

[0026] The copolymer (P) related to the present invention needs to contain at least one kind of each of the structural unit (A) and the structural unit (B), and includes a total of two or more monomer units, and may contain other structural units (C). The structural units and the amounts of the structural units of the copolymer (P) related to the present invention will be described. The structure derived from one molecule of each of ethylene and / or an α-olefin (A) having 3 to 20 carbon atoms, a monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group, and an arbitrary monomer (C) is defined as one structural unit in the copolymer (P). And when the total of the structural units in the copolymer (P) is 100 mol%, the ratio of each structural unit expressed in mol% is the amount of the structural unit.

[0027] · Amount of the structural unit of ethylene and / or an α-olefin having 3 to 20 carbon atoms (A): The amount of the structural unit (A) related to the present invention has a lower limit of 60.0 mol% or more, preferably 70.0 mol% or more, more preferably 80.0 mol% or more, still more preferably 85.0 mol% or more, even more preferably 90.0 mol% or more, particularly preferably 95.0 mol% or more, and an upper limit selected from 99.0 mol% or less, preferably 98.0 mol% or less, more preferably 97.0 mol% or less, still more preferably 96.5 mol% or less. If the amount of structural units derived from ethylene and / or α-olefins (A) having 3 to 20 carbon atoms is less than 60.0 mol%, the rigidity of the ionomer produced from the copolymer (P) may be inferior. If it is more than 99.0 mol%, the crystallinity of the ionomer produced from the copolymer (P) may increase and the flexibility may decrease.

[0028] · Amount of structural units of monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group: The amount of structural units of the structural unit (B) related to the present invention has a lower limit of 1.0 mol% or more, preferably 2.0 mol% or more, more preferably 3.0 mol% or more, still more preferably 3.5 mol% or more, and an upper limit of 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 13.0 mol% or less, still more preferably 10.0 mol% or less, particularly preferably 9.0 mol% or less, and most preferably 8.0 mol% or less. If the amount of structural units derived from the monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group is less than 1.0 mol%, the formation of ionic crosslinks may be reduced, resulting in sagging. If it is more than 20.0 mol%, sufficient mechanical properties of the copolymer (P) may not be obtained. Furthermore, the monomer having a carboxyl group and / or a dicarboxylic anhydride group used may be used alone or in combination of two or more.

[0029] · Amount of structural units of other monomers (C): The amount of structural units of the structural unit (C) related to the present invention has an upper limit selected from 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, still more preferably 8.0 mol% or less, and particularly preferably 5.0 mol% or less. There is no particular limitation on the lower limit, and it may be 0 mol%. When the amount of structural units derived from any monomer (C) is 20.0 mol% or less, sufficient mechanical properties of the copolymer (P) are easily obtained. Furthermore, any monomer (C) used may be used alone or in combination of two or more.

[0030] · Number of branches per 1,000 carbons in the copolymer (P): In the copolymer (P) of the present invention, when copolymerized substantially linearly, 13 the number of methyl branches calculated by C-NMR may have an upper limit of 50 or less, 5.0 or less, 1.0 or less, or 0.5 or less per 1,000 carbons, and the lower limit is not particularly limited, and the less the better. Also, the number of ethyl branches may have an upper limit of 3.0 or less, 2.0 or less, 1.0 or less, or 0.5 or less per 1,000 carbons, and the lower limit is not particularly limited, and the less the better. Further, the number of butyl branches may have an upper limit of 7.0 or less, 5.0 or less, 3.0 or less, or 0.5 or less per 1,000 carbons, and the lower limit is not particularly limited, and the less the better. When copolymerized substantially linearly, better mechanical properties can be obtained compared to branched copolymers.

[0031] · Method for measuring the amount of structural units and the number of branches derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups, and acyclic monomers in the copolymer (P): The amount of structural units and the number of branches per 1,000 carbons derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups, and acyclic monomers in the copolymer (P) of the present invention are 13 determined using a C-NMR spectrum. 13 C-NMR is measured by the following method. 200 - 300 mg of the sample is placed in a mixed solvent of o-dichlorobenzene (C 6 H 4 Cl 2 ) and deuterated benzene bromide (C 6 D 5 Br) (C 6 H 4 Cl 2 / C 6 D 5Br = 2 / 1 (volume ratio)) 2.4 ml was placed in an NMR sample tube with an inner diameter of 10 mm φ together with hexamethyldisiloxane, which is a reference substance for chemical shift, and after nitrogen substitution, the tube was sealed, heated and dissolved to obtain a uniform solution as an NMR measurement sample. The NMR measurement is carried out at 120 °C using an AV400M type NMR apparatus of Bruker Japan Co., Ltd. equipped with a 10 mm φ cryoprobe. 13 C-NMR is measured by the inverse gate decoupling method at a sample temperature of 120 °C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and an integration number of 512 times or more. The chemical shift is based on the 13 C signal of hexamethyldisiloxane set at 1.98 ppm, and the chemical shift of the signal due to other 13 C is used as a reference. The obtained 13 In the 13C-NMR, by identifying the signals specific to the monomers or branches of the copolymer (P) and comparing their intensities, the amount of structural units of each monomer and the number of branches in the copolymer (P) can be analyzed. The positions of the signals specific to the monomers or branches can be referred to known materials or can be identified independently according to the sample. Such an analysis method can be generally carried out by those skilled in the art.

[0032] · Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn): The weight average molecular weight (Mw) of the copolymer (P) according to the present invention usually has a lower limit of 1,000 or more, preferably 6,000 or more, more preferably 10,000 or more, and an upper limit of usually 2,000,000 or less, preferably 1,500,000 or less, still more preferably 1,000,000 or less, particularly preferably 800,000 or less, and most preferably 100,000 or less. When Mw is less than 1,000, the physical properties such as the mechanical strength and impact resistance of the copolymer (P) may not be sufficient. When Mw exceeds 2,000,000, the melt viscosity of the copolymer (P) becomes very high, and the molding process of the copolymer (P) may become difficult.

[0033] The ratio (Mw / Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the copolymer (P) according to the present invention is usually in the range of 1.5 to 4.0, preferably 1.6 to 3.7, more preferably 1.7 to 3.5, and still more preferably 1.9 to 2.4. When Mw / Mn is less than 1.5, various processabilities such as molding of the copolymer (P) may not be sufficient. When it exceeds 4.0, the mechanical properties of the copolymer (P) may be inferior. In the present invention, (Mw / Mn) may be expressed as a molecular weight distribution parameter.

[0034] The weight-average molecular weight (Mw) and the number-average molecular weight (Mn) according to the present invention are determined by gel permeation chromatography (GPC). Further, the molecular weight distribution parameter (Mw / Mn) is obtained by gel permeation chromatography (GPC), and further the number-average molecular weight (Mn) is determined, and the ratio of Mw to Mn, Mw / Mn, is calculated.

[0035] An example of the measurement method of GPC according to the present invention is as follows. (Measurement conditions) Model used: GPC-IR manufactured by Polymer Char Detector: IR-6 manufactured by Polymer Char Measurement temperature: 145 °C Solvent: ortho-dichlorobenzene (ODCB) Column: HT-806 (two columns) manufactured by Resonac Flow rate: 1.0 mL / min Injection volume: 0.2 mL (Preparation of sample) The sample is prepared as a 1 mg / mL solution using ODCB (containing 0.5 mg / mL of BHT (2,6-di-t-butyl-4-methylphenol)), and it takes about 1 hour to dissolve at 140 °C. (Calculation of molecular weight (M)) It is carried out by the standard polystyrene method, and the conversion from retention volume to molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The standard polystyrene to be used is, for example, the products of Tosoh Corporation, with the brands of (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000), or the monodisperse polystyrene (S-3210, S-1570, S-607, S-298, S-129, S-49, S-17, S-6.3, S-3.3, S-1.2, each 0.05 mg / ml solution) manufactured by Resochm etc. A solution dissolved in ODCB (containing 0.5 mg / mL of BHT) so that each becomes 0.5 mg / mL is injected in an amount of 0.2 mL to create a calibration curve. As the calibration curve, a cubic equation approximated by the least squares method, or one approximated by a quartic equation for the elution time and the logarithmic value of the molecular weight is used. For the viscosity formula [η]=K×Mα used for the conversion to the molecular weight (M), the following numerical values are used. Polystyrene (PS): K = 1.38×10 -4 , α = 0.7 Polyethylene (PE): K = 3.92×10 -4 , α = 0.733 Polypropylene (PP): K = 1.03×10 -4 , α = 0.78

[0036] ·Melting point (Tm, °C): The melting point of the copolymer (P) according to the present invention is indicated by the maximum peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). The maximum peak temperature means, in the DSC measurement, when a plurality of peaks are shown in the endothermic curve obtained with the heat flow (mW) on the vertical axis and the temperature (°C) on the horizontal axis, it indicates the temperature of the peak with the maximum height from the baseline among them, and when there is one peak, it indicates the temperature of that peak. In the present invention, the melting point can be determined, for example, using a DSC (DSC7020) manufactured by SII NanoTechnology Inc., filling about 5.0 mg of the sample in an aluminum pan, heating to 200 °C at 10 °C / min, holding isothermally at 200 °C for 5 minutes, then cooling to 20 °C at 10 °C / min, holding isothermally at 20 °C for 5 minutes, and then heating to 200 °C again at 10 °C / min from the absorption curve.

[0037] ·Degree of crystallinity (%): In the copolymer (P) of the present invention, the degree of crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but it is preferably more than 0%. It is more preferably more than 5%, and still more preferably 7% or more. When the degree of crystallinity is 0%, the rigidity of the copolymer (P) may not be sufficient. The degree of crystallinity is also an index of flexibility, and flexibility is preferable, but the upper limit of the degree of crystallinity is not particularly limited. In the present invention, the degree of crystallinity can be determined, for example, by obtaining the heat of fusion (ΔH) from the area of the endothermic peak of fusion obtained by DSC measurement in the same procedure as the measurement of the melting point described above, and dividing the heat of fusion by the heat of fusion of a completely crystalline high-density polyethylene (HDPE) of 293 J / g.

[0038] ·Molecular structure: The molecular chain end of the copolymer (P) according to the present invention may be a structural unit (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms, a structural unit (B) of a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group, or a structural unit (C) of an arbitrary monomer.

[0039] Further, the copolymer (P) according to the present invention includes a random copolymer, a block copolymer, etc. of a structural unit (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms, a structural unit (B) of a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group, and a structural unit (C) of an arbitrary monomer. Among these, a random copolymer capable of containing a large amount of the structural unit (B) may be used. A molecular structure example (1) of a general ternary copolymer (P) is shown below. A random copolymer is a copolymer in which the probability of finding the structural units (A) of ethylene and / or α-olefins having 3 to 20 carbon atoms, the structural units (B) of monomers having a carboxyl group and / or a dicarboxylic anhydride group, and the structural units (C) of any monomers at a position in any molecular chain is independent of the type of the adjacent structural units. As shown below, in the molecular structure example (1) of the copolymer, the structural units (A) of ethylene and / or α-olefins having 3 to 20 carbon atoms, the structural units (B) of monomers having a carboxyl group and / or a dicarboxylic anhydride group, and the structural units (C) of any monomers form a random copolymer.

Chemical formula

[0040] In addition, although the random copolymerizability in the copolymer (P) can be confirmed by various methods, a method for discriminating random copolymerizability from the relationship between the comonomer content and the melting point of the copolymer (P) is described in detail in JP-A-2015-163691 and JP-A-2016-079408. When the melting point (Tm, °C) of the copolymer is higher than -3.74×[Z]+130 (where [Z] is the comonomer content / mol%), it can be judged that the random copolymerizability is low.

[0041] For the copolymer (P) according to the present invention which is a random copolymer, it is preferable that the melting point (Tm, °C) observed by differential scanning calorimetry (DSC) and the total content [Z] (mol%) of the structural units (B) of monomers having a carboxyl group and / or a dicarboxylic anhydride group and the structural units (C) of any monomers satisfy the following formula (I). 50<Tm<-3.74×[Z]+130···(I) When the melting point (Tm, °C) of the copolymer (P) is higher than -3.74×[Z]+130 (°C), the random copolymerizability is low, and thus the mechanical properties such as impact strength may be inferior. When the melting point is lower than 50 °C, the rigidity may be inferior.

[0042] Furthermore, when the molecular structure of the copolymer (P) according to the present invention is linear, it is preferably produced in the presence of a transition metal catalyst. On the other hand, the branched copolymer is produced by a production method such as polymerization by a high-pressure radical polymerization process or polymerization using a metal catalyst. Although the difference in this molecular structure can be controlled by selecting the production method, for example, as described in JP-A-2010-150532, the molecular structure can also be estimated from the complex elastic modulus measured with a rotational rheometer.

[0043] · Absolute value G of complex elastic modulus * = Phase angle δ at 0.1 MPa: Absolute value G of complex elastic modulus measured with a rotational rheometer * = Phase angle δ at 0.1 MPa (G * = 0.1 MPa) is 50 degrees or more, the molecular structure of the copolymer is a linear structure. Also, the absolute value G of the complex elastic modulus measured with a rotational rheometer * = Phase angle δ at 0.1 MPa (G * = 0.1 MPa) is less than 50 degrees, the molecular structure of the copolymer shows a structure containing an excessive amount of long-chain branches. Absolute value G of complex elastic modulus measured with a rotational rheometer * = Phase angle δ at 0.1 MPa is affected by both the molecular weight distribution and the amount of long-chain branches. However, for the copolymer (P) with Mw / Mn ≤ 4, more preferably Mw / Mn ≤ 3, it serves as an index for the amount of long-chain branches, and the more long-chain branches contained in its molecular structure, the smaller the δ (G * = 0.1 MPa) value becomes. In addition, if Mw / Mn of the copolymer (P) is 1.5 or more, even when the molecular structure does not contain long-chain branches, the δ (G * = 0.1 MPa) value does not exceed 75 degrees.

[0044] The method for measuring the complex elastic modulus is as follows. Place the sample into a heating press mold with a thickness of 1.0 mm. After preheating in a hot press machine with a surface temperature of 180 °C for 5 minutes, degas the residual gas in the molten resin by repeating pressurization and depressurization, then pressurize at 4.9 MPa and hold for 5 minutes. Thereafter, transfer the sample to a press machine with a surface temperature of 25 °C and cool it by holding at a pressure of 4.9 MPa for 3 minutes to produce a press plate composed of a sample with a thickness of approximately 1.0 mm. Use a press plate made of the sample processed into a 25-mm diameter circle as a sample, and use an MCR type rotary rheometer manufactured by Anton Paar as a measuring device for dynamic viscoelastic properties, and measure the dynamic viscoelasticity under the following conditions in a nitrogen atmosphere. · Plate: φ25 mm parallel plate · Temperature: 160 °C · Strain amount: 10% · Measurement angular frequency range: 1.0×10 -2 ~1.0×10 2 rad / s · Measurement interval: 5 points / decade Absolute value G of complex elastic modulus * (Pa) of common logarithm logG * Plot the phase angle δ against it, and the value of δ (degree) at the point corresponding to logG * =5.0 is defined as δ(G * =0.1 MPa). When there is no point corresponding to logG * =5.0 among the measurement points, use two points around logG * =5.0 to obtain the δ value at logG * =5.0 by linear interpolation. Also, when all the measurement points are logG * <5, use the values of three points from the ones with larger logG * values to extrapolate the δ value at logG * =5.0 by a quadratic curve.

[0045] · Regarding the production of copolymer (P) The copolymer (P) having a substantially linear structure according to the present invention is preferably produced in the presence of a transition metal catalyst. On the other hand, the copolymer (P) having a branched structure according to the present invention is produced by a production method such as polymerization by a high-pressure radical polymerization process or polymerization using a metal catalyst.

[0046] · Coordination catalyst The type of the coordination catalyst used for the production of the substantially linear copolymer (P) according to the present invention is not particularly limited as long as it can copolymerize the structural unit (A), the structural unit (B), and the optional structural unit (C). Examples thereof include transition metal compounds of Groups 5 to 11 having a chelating ligand. Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, copper atom and the like. Among these, preferred are transition metals of Groups 8 to 11, more preferred are transition metals of Group 10, and particularly preferred are nickel (Ni) and palladium (Pd). These metals may be used singly or in combination of two or more. The chelating ligand has at least two atoms selected from the group consisting of P, N, O, and S, and includes a ligand that is bidentate or multidentate and is electronically neutral or anionic. The structure of the chelating ligand is exemplified in the review by Brookhart et al. (Chem. Rev., 2000, 100, 1169). Preferred examples of the chelating ligand include bidentate anionic P, O ligands. Examples of the bidentate anionic P, O ligands include phosphinosulfonic acid, phosphinocarboxylic acid, phosphinophenol, and phosphinoenolate. Other examples of the chelating ligand include bidentate anionic N, O ligands. Examples of the bidentate anionic N, O ligands include salicylaldiminato and pyridinecarboxylic acid. Other examples of the chelating ligand include diimine ligands, diphenoxide ligands, and diamide ligands.

[0047] The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (a) or (b) coordinated with an arylphosphine compound, an arylarsine compound, or an arylantimony compound which may have a substituent. [Chemical formula] [Chemical formula] In structural formula (a) and structural formula (b), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of elements, that is, various transition metals as described above. X 1 represents oxygen, sulfur, -SO 3 -, or -CO 2 -. Y 1 represents carbon or silicon. n represents an integer of 0 or 1. E 1 represents phosphorus, arsenic, or antimony. R 53 and R 54 each independently represent hydrogen or a hydrocarbon group which may contain heteroatoms and has 1 to 30 carbon atoms. R 55 each independently represent hydrogen, a halogen, or a hydrocarbon group which may contain heteroatoms and has 1 to 30 carbon atoms. R 56 and R 57 each independently represent hydrogen, a halogen, a hydrocarbon group which may contain heteroatoms and has 1 to 30 carbon atoms, OR 52 CO 2 R 52 CO 2 M', C(O)N(R 51 ) 2 C(O)R 52 SR 52 SO 2 R 52 SOR 52 OSO 2 R 52 P(O)(OR 52 ) 2-y (R 51 ) y CN, NHR 52 N(R 52 ) 2, Si(OR 51 ) 3-x (R 51 ) x , OSi(OR 51 ) 3-x (R 51 ) x , NO 2 , SO 3 M’, PO 3 M’ 2 , P(O)(OR 52 ) 2 M’ or represents an epoxy-containing group. R 51 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 52 represents a hydrocarbon group having 1 to 20 carbon atoms. M’ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2. Note that R 56 and R 57 may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, or sulfur. At this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent. L 1 represents a ligand coordinated to M. Also, R 53 and L 1 may bond to each other to form a ring.]

[0048] More preferably, it is a transition metal complex represented by the following structural formula (c).

Chemical formula

[0049] Here, as the catalyst of the transition metal compound of Groups 5 to 11 having a chelating ligand, typically, catalysts such as so-called SHOP catalysts and Drent catalysts are known. The SHOP catalyst is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to a nickel metal (see, for example, WO2010-050256). Also, the Drent catalyst is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to a palladium metal (see, for example, JP-A-2010-202647).

[0050] · Polymerization method of the copolymer (P): The polymerization method of the copolymer (P) according to the present invention is not limited. Examples of the polymerization method include slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization carried out in a vaporized monomer, or high-pressure ionic polymerization in which at least a part of the produced polymer is dissolved in the monomer liquefied at high temperature and high pressure. The polymerization form may be any of batch polymerization, semi-batch polymerization, or continuous polymerization. Also, living polymerization may be carried out, or polymerization may be carried out while concurrent chain transfer occurs. Furthermore, during polymerization, a so-called chain shuttling agent (CSA) may be used in combination to carry out a chain shuttling reaction or coordinative chain transfer polymerization (CCTP). Regarding specific manufacturing processes and conditions, they are disclosed in, for example, JP-A-2010-260913 and JP-A-2010-202647.

[0051] · Method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the copolymer (P): The method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the copolymer (P) according to the present invention is not particularly limited. Within the scope not departing from the gist of the present invention, a carboxyl group and / or a dicarboxylic acid anhydride group can be introduced by various methods. Examples of the method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group include a method of directly copolymerizing a comonomer having a carboxyl group and / or a dicarboxylic acid anhydride group, and a method of introducing a carboxyl group and / or a dicarboxylic acid anhydride group by modification after copolymerizing other monomers.

[0052] As a method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group by modification, for example, when introducing a carboxylic acid, a method of hydrolyzing an acrylate ester after copolymerization to change it into a carboxylic acid, or a method of changing it into a carboxylic acid by thermal decomposition after copolymerizing t-butyl acrylate, etc. can be mentioned. The precursor before modification of the copolymer (P) which is the base resin of the ionomer obtained by modification is called an ionomer base resin precursor.

[0053] When performing hydrolysis or thermal decomposition as described above, a conventionally known acid-base catalyst may be used as an additive to accelerate the reaction. The acid-base catalyst is not particularly limited, and examples thereof include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; carbonates of alkali metals and alkaline earth metals such as sodium hydrogen carbonate and sodium carbonate; solid acids such as montmorillonite; inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; and organic acids such as formic acid, acetic acid, benzoic acid, citric acid, p-toluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid, which can be appropriately used. From the viewpoints of reaction acceleration effect, price, apparatus corrosiveness, etc., sodium hydroxide, potassium hydroxide, sodium carbonate, p-toluenesulfonic acid, and trifluoroacetic acid are preferred, and p-toluenesulfonic acid and trifluoroacetic acid are more preferred.

[0054] (6) Ionomer The ionomer according to the present invention is an ionomer in which at least a part of the carboxyl group and / or dicarboxylic anhydride group of the structural unit (B) of the copolymer (P) of the present invention is converted into a metal-containing carboxylate containing at least one kind of metal ion.

[0055] · Structure of ionomer The ionomer according to the present invention is preferably an ionomer having a substantially linear structure. When the copolymer (P) has a linear structure, the absolute value G of the complex elastic modulus measured with a rotational rheometer is the same as that in the case where the copolymer (P) has a linear structure. * The phase angle δ at G = 0.1 MPa is in the range of 50 degrees to 75 degrees. When the phase angle δ (G = 0.1 MPa) is lower than 50 degrees, the molecular structure of the ionomer shows a structure containing an excessive amount of long-chain branches. Also, even when the molecular structure does not contain long-chain branches, the δ (G = 0.1 MPa) value does not exceed 75 degrees. * = 0.1 MPa) is lower than 50 degrees, the molecular structure of the ionomer shows a structure containing an excessive amount of long-chain branches. Also, even when the molecular structure does not contain long-chain branches, the δ (G * = 0.1 MPa) value does not exceed 75 degrees. When the ionomer of the present invention is substantially linear, from the viewpoint of improving mechanical strength, the lower limit of the phase angle δ is preferably 51 degrees or more, more preferably 54 degrees or more, still more preferably 56 degrees or more, and even more preferably 58 degrees or more. The upper limit is not particularly limited, and the closer to 75 degrees, the better.

[0056] · Metal ion The metal ions contained in the ionomer according to the present invention can include the metal ions used in conventionally known ionomers. The metal ions are not particularly limited, but include Li + , Na + , K + , Rb + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ , Zn 2+ , Rb + , Ca 2+ , Be 2+ , Sr 2+ , Ba 2+ , Al 3+ , Sc 3+ , Ti 2+ , Ti 3+ , Ti 4+ , V 5+ , Cr 2+ , Cr 3+ , Cr 6+ , Mn 7+ , Fe 2+ , Fe 3+ , Co + , Co 2+ , Co 3+ , Ga 2+ , Ga 3+ , La 3+ , Ce 4+ , Pr 3+ , Pr 4+ , Nd 3+ , Mo 3+ , Mo 4+ , Mo 5+ , Mo 6+ , Ag + are mentioned. Also, instead of metal ions, NH 4+ It can also be used. Among the metal ions, those of Group 1, Group 2 or Group 12 of the periodic table are preferably used, and Li + , Na + , K + , Rb + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ , Zn 2+ At least one selected from the group consisting of is more preferable. Particularly preferably, Na + , K + , Mg 2+ , Ca 2+ , Ba 2+ and Zn 2+ , More preferably, at least one selected from the group consisting of Na + , Mg 2+ and Ca 2+ is mentioned. These metal ions can be mixed and contained in two or more kinds as necessary.

[0057] ·Degree of neutralization (%) As the content of the metal ions, it is preferably included in an amount that neutralizes at least a part or all of the carboxyl groups and / or dicarboxylic anhydride groups in the copolymer (P) as the base polymer. The preferable degree of neutralization (average degree of neutralization) is 1 to 90%, more preferably 5 to 85%, and still more preferably 10 to 70%. Since the dicarboxylic anhydride group forms a carboxylate salt and opens the ring to become a dicarboxylic acid, the total mol amount of the carboxyl groups is determined as having 2 mol of carboxyl groups per 1 mol of the dicarboxylic anhydride group. Also, for example, divalent metal ions such as Zn 2+ etc. are assumed to form a salt with 2 mol of carboxyl groups per 1 mol, and the total mol amount of the molecules of the degree of neutralization is calculated by 2 × mol amount. When the degree of neutralization is high, the tensile strength and tensile fracture stress of the ionomer are high, and the tensile fracture strain is small, but the melt flow rate (MFR) of the ionomer tends to be small. On the other hand, when the degree of neutralization is low, an ionomer with a moderate MFR and a low tensile modulus can be obtained, but the tensile fracture stress is low and the tensile fracture strain tends to be high. When the degree of neutralization is less than 1%, the toughness (strength and impact resistance) of the ionomer may be insufficient, and when the degree of neutralization is higher than 90%, the fluidity may be insufficient.

[0058] · Neutralization amount (mol%) The neutralization amount is the amount of carboxylic acid groups neutralized by metal ions, that is, the content of metal-containing carboxylate groups in the ionomer, and can be obtained from the ratio of the total mol amount of the valence number × mol amount of metal ions to the total mol amount of carboxyl groups that may be contained in the carboxyl groups and / or dicarboxylic anhydride groups in the copolymer (P). The ionomer of the present invention has a neutralization amount of 0.4 to 10 mol%. Although the ionomer contains metal ions in the polymer, at a low temperature state where it does not melt, the momentum of the molecules decreases, and at the same time, the metal ions form pseudo-crosslinks, contributing to an increase in viscosity. In addition, this pseudo-crosslinked structure makes the molecular structure network-like and also contributes to an improvement in impact strength. On the other hand, in the case of a non-ionomer, the carboxylic acid groups in the polymer participate in crystal formation and become a factor in volume change, but in the ionomer, the pseudo-crosslinking by metal ions inhibits crystal formation, so there is an effect of suppressing volume change, that is, warpage. Also, when the amount of pseudo-crosslinking is small, the viscosity change during cooling becomes small, and the activation energy of flow tends to decrease. From the viewpoint of further improving the moldability as a resin for 3D printers and the strength of molded products, the neutralization amount in the ionomer is preferably 0.75 to 9.0 mol%, and more preferably 1.0 to 8.0 mol%. The neutralization amount of the ionomer can be calculated from the above-mentioned degree of neutralization and the amount of structural unit (B) in the ionomer base resin, and is obtained by [structural unit amount of structural unit (B) (mol%) × degree of neutralization (%) / 100].

[0059] · Crystallinity (%) of the ionomer: In the ionomer of the present invention, the crystallinity observed by differential scanning calorimetry (DSC) is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less in order to achieve good dimensional stability during molding. When it is 50% or more, shrinkage may occur due to a large amount of crystalline portions, resulting in poor dimensional stability. Also, from the viewpoint of sufficient rigidity of the ionomer, the lower limit is preferably more than 0%, more preferably more than 5%, and still more preferably 7% or more. When it is 0% or less, molding may be difficult because the rigidity is insufficient for molding.

[0060] · Melting point (Tm, °C) of the ionomer In the ionomer of the present invention, the melting point observed by differential scanning calorimetry (DSC) is not particularly limited, but is preferably 130°C or lower. It is more preferably 125°C or lower, and still more preferably 120°C or lower. When the melting point exceeds 130°C, the toughness is insufficient, which may affect physical properties such as the impact resistance of the ionomer. Also, as the lower limit of the melting point of the ionomer, it is preferably 60°C or higher, more preferably 70°C or higher, and still more preferably 75°C or higher. When the melting point is 60°C or lower, the balance between the comonomer content and the neutralization degree is not good, and the fluidity may decrease, causing molding defects.

[0061] · Tensile elastic modulus (MPa) of the ionomer In the ionomer of the present invention, the tensile modulus measured in accordance with Annex of JIS K6922-2:2018 is preferably 1800 MPa or less. More preferably, it is 1500 MPa or less, still more preferably 1300 MPa or less, further preferably 1000 MPa or less, still more preferably 800 MPa or less, and even more preferably 600 MPa or less. The tensile modulus of PLA resin generally used as a 3D printing material is about 2000 MPa, and that of ABS resin is about 3500 MPa. Since these materials have too high rigidity of the molded product, there is a concern about safety. When the tensile modulus is within this range, it is preferable because it has flexibility and can be used for a wide range of applications from the viewpoint of safety.

[0062] · Tensile impact strength of ionomer (J / m 2 ) In the ionomer of the present invention, the tensile impact strength measured by Method B of JIS K 7160-1996 is preferably 40 kJ / m 2 or more. More preferably, it is 50 kJ / m 2 or more, still more preferably 100 kJ / m 2 or more, further preferably 150 kJ / m 2 and even more preferably 200 kJ / m 2 or more. Particularly preferably, it is 40 kJ / m 2 If it is less than this, the strength is insufficient and the risk of breakage when dropped is high.

[0063] · Activation energy of ionomer flow (kJ / mol) In the ionomer of the present invention, the activation energy of flow measured by a rotational rheometer is preferably 40 kJ / mol or more, more preferably 45 kJ / mol or more, still more preferably 50 kJ / mol or more, and particularly preferably 55 kJ / mol or more. The activation energy of flow is a parameter that can be associated with the occurrence of sagging when the composition is applied. When the activation energy of flow is within this range, during the lamination of the resin, the flow of the already laminated resin in the time until the next layer is laminated is suppressed, and even when the molten resin is laminated on the layer, sagging is less likely to occur, so it is preferable from the viewpoint that a molded product as designed can be shaped.

[0064] Here, the activation energy of flow of the ionomer in this specification will be described. Regarding the activation energy of flow, (i) As a theoretical basis, the activation energy of flow is described, for example, in "Polymer Experimentation, Volume 9, Mechanical Properties I, published by Kyoritsu Shuppan Co., Ltd. (1985), pages 25 to 28, edited by the Polymer Society's Polymer Experimentation Editorial Committee", and by measuring the viscoelastic frequency dependence and using the shift factor a T the activation energy of flow can be determined. (ii) As a method for measuring the activation energy of flow, fix a graph of the relationship between the storage modulus (vertical axis) measured at a certain reference temperature and the angular velocity (horizontal axis), and when moving the data measured at another measurement temperature parallel to the horizontal axis, it can be superimposed on the data at the reference temperature. The shift factor a T is the amount log(a T ) by which the data at each measurement temperature is shifted to be superimposed on the data at the reference temperature according to the Arrhenius equation. The activation energy of flow can be determined from the slope of the straight line obtained by plotting it against the reciprocal 1 / T of the measurement temperature (absolute temperature). (iii) In a specific measurement, a resin to be tested, which is press-molded into a circular shape with a diameter of 25 mm and a thickness of 1 mm at 180 °C, is used as a sample. The measuring device for dynamic viscoelastic properties uses a UDS-200 type rotary rheometer manufactured by Paar Physica and a 25 mmφ parallel plate, and measures the dynamic viscoelasticity at temperatures (140 °C, 170 °C, 190 °C, 210 °C, and 230 °C) under the following conditions in a nitrogen atmosphere. Strain amount: 10% Measurement frequency range: 6.22×10 -3 ~6.22×10 2 rad / s (at 210 °C and 230 °C, 6.22×10 -2 ~6.22×10 2 rad / s) Taking 190 °C as the reference temperature, the storage modulus G' and loss modulus G" under five temperature conditions are superimposed according to the principle of time-temperature superposition to obtain the shift factor a T . This shift factor is plotted against the reciprocal of the absolute temperature, and the activation energy Ea for flow is calculated from the slope.

[0065] In the present invention, the activation energy for flow is measured by a rotary rheometer. An example of the method for measuring the activation energy for flow is as follows. Place the sample into a heating press mold with a thickness of 1.0 mm. After preheating in a hot press machine with a surface temperature of 180 °C for 5 minutes, degas the residual gas in the molten resin by repeating pressurization and depressurization, then pressurize at 4.9 MPa and hold for 5 minutes. Then, transfer the sample to a press machine with a surface temperature of 25 °C and cool it by holding at a pressure of 4.9 MPa for 3 minutes to create a press plate composed of a sample with a thickness of approximately 1.0 mm. A sample obtained by processing the press plate made of the sample into a 25 mm diameter circle is selected as a sample. Select the MCR type of Anton Raar as a rotational rheometer, gas-seal the rheometer's test chamber with nitrogen to minimize polymer degradation. After preheating the rheometer to the test temperature, load the sample to obtain the thermal equilibrium of the oven. Clamp the test piece between parallel plates to a thickness of 1.0 mm, cut off the excess, and then measure the complex viscosity by performing small strain (10%) oscillatory shear measurement. By performing the measurement operation of compatibility at multiple test temperatures, the complex viscosity for each angular frequency at each temperature can be obtained. The measurement interval of the measurement temperature is about 10 - 20 °C and measure at three or more points. Obtain an approximate straight line from the Arrhenius plot of the obtained numerical values by a fixed method, and calculate the activation energy Ea (kJ / mol) of flow from the slope of the straight line. · Plate: φ25 mm parallel plate · Temperature: 140, 160, 180 °C · Strain amount: 10% · Measurement angular frequency range: 1.0×10 -2 ~1.0×10 2 rad / s · Measurement interval: 5 points / decade

[0066] · Moldability The formability in the present invention is indicated by the fluidity of the resin, the degree of shrinkage leading to warping, and the sagging when forming fine details during the process of extruding the molten resin and then cooling it in 3D printing by the material extrusion method. The warping referred to in this application means a state in which a part on either the long side or the short side of a flat plate formed on a flat granite plate floats above the granite plate surface. If the warping is too large, during the forming process, the formed object floats above the designed position, preventing the next layer from being laminated at the designed position, or the nozzle for laminating the next layer interferes with the formed object floating above the designed position due to warping, resulting in poor forming. Also, in this specification, "sagging" refers to the occurrence of poor forming when, during the formation of fine parts, the time until the next layer is laminated is short, molten resin is laminated on a layer where the resin has not solidified sufficiently, and the shape cannot be maintained due to its own weight.

[0067] The fluidity of the resin can be represented by the melt flow rate (MFR) measured in accordance with JIS K-7210 (1999). It is desirable that the melt flow rate measured under the conditions of a temperature of 190°C and a load of 21.18 N (= 2.16 kg) in accordance with JIS-K6922-2:2018 is 0.01 or more. More preferably, it is 0.1 or more, still more preferably 0.5 or more, and preferably 1.0 or more. If the melt flow rate is less than 0.01, the viscosity is high, resulting in poor fluidity, which may cause clogging of the nozzle and poor forming.

[0068] The degree of shrinkage during the curing of the resin can be represented by the shrinkage rate measured in accordance with JIS K 7152-4:2006. The shrinkage rate measured in accordance with JIS K 7152-4:2006 is preferably 2.2% or less. It is preferably 2.0% or less, more preferably 1.8% or less, even more preferably 1.6% or less, and even more preferably 0% or more and 1.4% or less. Since the resin for 3D printers of the present invention contains the copolymer (P) of ethylene and an α-olefin having 3 to 12 carbon atoms, the shrinkage rate will not be less than 0%. When the shrinkage rate is within this range, the dimensional change generated during cooling is small, so it is preferable because a shaped article as designed can be formed.

[0069] · Method for producing ionomer The ionomer related to the present invention may be obtained by subjecting a copolymer (P) of ethylene and / or an α-olefin / unsaturated carboxylic acid having 3 to 20 carbon atoms to a conversion step of treating with a metal salt containing at least one kind of metal ion to convert it into a metal-containing carboxylate. Further, the ionomer related to the present invention may be obtained by heating an ethylene and / or an α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms and subjecting at least a part of the ester groups in the copolymer to a heat conversion step of converting them into a metal-containing carboxylate containing at least one kind of metal ion. In addition, the copolymer which is the raw material resin used for the production of the ionomer related to the present invention may be one kind of the copolymer (P) or may contain two or more kinds.

[0070] In order to produce an ionomer after introducing a carboxyl group and / or a dicarboxylic anhydride group into the copolymer (P), for example, the following method can be adopted. That is, an ionomer can be produced by heating and kneading a substance that captures metal ions, such as an ethylene / (meth)acrylic acid copolymer, and a metal salt as appropriate.

[0071] In the heat conversion step, an ethylene and / or C3-20 α-olefin / unsaturated carboxylic acid ester copolymer is heated and converted into an ethylene and / or C3-20 α-olefin / unsaturated carboxylic acid copolymer (P) by hydrolysis or thermal decomposition, and then reacted with a compound containing metal ions, whereby the carboxylic acid in the ethylene and / or C3-20 α-olefin / unsaturated carboxylic acid copolymer (P) may be converted into the metal-containing carboxylate. Alternatively, an ethylene and / or C3-20 α-olefin / unsaturated carboxylic acid ester copolymer is heated and reacted with a compound containing metal ions while hydrolyzing or thermally decomposing the ester groups of the copolymer, whereby the ester group portion in the ethylene and / or C3-20 α-olefin / unsaturated carboxylic acid ester copolymer may be converted into the metal-containing carboxylate. The compound containing metal ions herein is preferably a compound containing metal ions of Group 1, Group 2 or Group 12 of the periodic table.

[0072] Furthermore, the compound containing metal ions may be a metal oxide, hydroxide, carbonate, bicarbonate, acetate, formate, or the like. The compound containing metal ions may be supplied to the reaction system in granular or fine powder form, or may be dissolved or dispersed in water or an organic solvent and then supplied to the reaction system. A masterbatch based on an ethylene / unsaturated carboxylic acid copolymer or an olefin copolymer may be prepared and supplied to the reaction system. To smoothly proceed the reaction, it is preferable to prepare a masterbatch and supply it to the reaction system.

[0073] Furthermore, the reaction with the compound containing metal ions may be carried out by melt-kneading using various types of apparatuses such as a vent extruder, a Banbury mixer, and a roll mill, and the reaction may be either batchwise or continuous. By discharging volatile components such as water and carbon dioxide gas by-produced by the reaction using a degassing apparatus, the reaction can proceed smoothly, so it is preferable to carry out continuously using an extruder equipped with a degassing apparatus such as a vent extruder. When reacting with a compound containing metal ions, a small amount of water may be injected to accelerate the reaction.

[0074] The temperature for heating the ethylene and / or α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms may be any temperature at which the ester becomes a carboxylic acid. If the heating temperature is too low, the ester will not be converted into a carboxylic acid, and if it is too high, decarbonylation and decomposition of the copolymer will proceed. Therefore, the heating temperature of the present invention is preferably in the range of 80°C to 350°C, more preferably 100°C to 340°C, still more preferably 150°C to 330°C, and even more preferably 200°C to 320°C.

[0075] The reaction time varies depending on the heating temperature, the reactivity of the ester group portion, etc., but is usually 1 minute to 50 hours, more preferably 2 minutes to 30 hours, still more preferably 2 minutes to 10 hours, even more preferably 2 minutes to 3 hours, and particularly preferably 3 minutes to 2 hours.

[0076] In the above process, there is no particular limitation on the reaction atmosphere, but it is generally preferable to carry out the reaction under an inert gas stream. Examples of the inert gas that can be used include nitrogen, argon, and a carbon dioxide atmosphere. A small amount of oxygen or air may be mixed in.

[0077] The reactor used in the above process is not particularly limited, and it is not limited at all as long as it is a method capable of stirring the copolymer substantially uniformly. A glass container equipped with a stirrer or an autoclave (AC) may be used, or any conventionally known kneader such as a Brabender plastograph, a single-screw or twin-screw extruder, a powerful screw-type kneader, a Banbury mixer, a kneader, or a roll can also be used.

[0078] For the copolymer (P) of ethylene and / or an α-olefin having 3 to 20 carbon atoms / unsaturated carboxylic acid into which metal ions are introduced, whether it has become an ionomer can be confirmed by measuring the IR spectrum of the obtained resin and examining the decrease in the peak derived from the carbonyl group of the carboxylic acid (dimer). Similarly, the degree of neutralization can also be confirmed by examining the decrease in the peak derived from the carbonyl group of the carboxylic acid (dimer) and the increase in the peak derived from the carbonyl group of the carboxylate group, in addition to the calculation from the above-mentioned molar ratio.

[0079] <Resin for 3D printer> One aspect of the present invention is a resin composition for a 3D printer containing the above ionomer. As the resin for a 3D printer, the above ionomer may be used alone, or two or more kinds of ionomers may be mixed and used. In addition to the ionomer, a resin composition containing the above ionomer can be used. By including the ionomer of the present invention, a resin having the characteristics required for 3D printer applications, such as no warping, deformation, or sagging, can be provided, and a molded product excellent in the balance of moldability, impact strength, and flexibility, which could not be achieved with conventional 3D printing materials, can be formed.

[0080] An appropriate known thermoplastic resin can be mixed with the above ionomer and used as a resin for a 3D printer. As long as low crystallinity suitable for 3D printer applications can be ensured, a crystalline resin may be added. Examples of resins that can be mixed with the above ionomer include polyester, polyamide, polyimide, polyurethane, polyethylene, polyolefin or ethylene-α-olefin copolymer, terephthalic acid derivative resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene, polyacetal, polyacrylate or ethylene-(meth)acrylate copolymer, modified ethylene-(meth)acrylate copolymer, and halogenated polymers such as chlorinated polyethylene and polyvinyl chloride.

[0081] When the above ionomer is used by mixing with other resins, the blending ratio is such that when the total resin composition is 100 parts by mass, the content of the above ionomer is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. By using 50% by mass or more of the above ionomer, it is preferable because a molded product having high strength, flexibility, and impact resistance inherent to the ionomer can be shaped. If the content of the ionomer is less than 50% by mass, warping, sagging, and poor miscibility are a concern.

[0082] · Additive In the resin composition for a 3D printer according to the present invention, within a range not departing from the gist of the present invention, conventionally known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, colorants, pigments, crosslinking agents, foaming agents, nucleating agents, flame retardants, conductive materials, and additives usually used in resin compositions for 3D printers such as fillers may be blended. The use of these additives is appropriately selected according to the molding application.

[0083] The resin composition for a 3D printer according to the present invention can be obtained by kneading the above ionomer and, if necessary, other resins or additives by known means. The kneaded resin composition can be used in pellet form, but it may also be further processed into filament form.

[0084] The filament of the resin composition for a 3D printer can be molded by any method known in the art. For example, pellets of the resin composition containing the above ionomer are supplied to an extruder, melted at a temperature higher than the melting peak temperature of the above ionomer, extruded through a die in a molten state, and then cooled to form a filament of a desired diameter. The filament can be obtained as a filament of any diameter depending on the diameter of the die through which it is extruded, but the diameter of the filament is preferably in the range of 1.5 to 3.1 mm.

[0085] The resin composition containing the ionomer of the present invention can be used to form a molded article by a material extrusion method. Thereby, a molded article containing the resin containing the ionomer of the present invention can be formed using 3D printing technology. The method for forming a molded article by 3D printing includes a step of depositing the resin for a 3D printer containing the above ionomer in a plurality of layers using a 3D printer to form a molded article.

[0086] In the material extrusion method, filament-based shaping can be performed. In this method, the filament containing the above ionomer is supplied through a die heated to a sufficient temperature. The heating temperature is a temperature equal to or higher than the melting point of the above ionomer. By containing the above ionomer, even if newly melted resin is deposited on the layer immediately after laminating the layers, shaping defects such as sagging can be suppressed. The melted filament exits from the nozzle and is deposited in a multi-layer shape to form a desired molded article. The control of the deposition rate can be performed by changing the supply rate of the filament, the cross-sectional dimensions, and the movement speed of the nozzle and / or the molded article. Therefore, one aspect of the present invention relates to a 3D printer molded article in which the resin for a 3D printer containing the above ionomer is formed by the deposition of one or more lines by melted filament deposition.

[0087] The shaping of a molded article by 3D printing can also be performed by shaping the resin composition containing the above ionomer in pellet form using an extruder. In this method, pellets containing the above ionomer are introduced into a heated extruder, and the resin melted linearly is extruded from the extruder to form a multi-layer shape, thereby forming a desired molded article.

Examples

[0088] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The measurement and evaluation of physical properties in Examples and Comparative Examples were carried out by the methods shown below. In addition, "no data" in the table means unmeasured, and "not detected" means below the detection limit.

[0089] <Measurement and Evaluation> Measurement Method (1) Absolute value G of complex elastic modulus * = Measurement of phase angle δ (G * = 0.1 MPa) at 0.1 MPa The sample was placed in a heating press mold with a thickness of 1.0 mm, preheated in a hot press machine with a surface temperature of 180 °C for 5 minutes, and then the residual gas in the molten resin was degassed by repeating pressurization and depressurization. Further, it was pressurized at 4.9 MPa and held for 5 minutes. Then, it was transferred to a press machine with a surface temperature of 25 °C and cooled by holding at a pressure of 4.9 MPa for 3 minutes to produce a press plate made of a sample with a thickness of about 1.0 mm. A sample obtained by processing the press plate made of the sample into a 25 mm diameter circle was used, and a MCR type rotary rheometer manufactured by Anton Paar was used as a measuring device for dynamic viscoelastic properties, and the dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere. · Plate: φ25 mm (diameter) parallel plate · Temperature: 160 °C · Strain amount: 10% · Measurement angular frequency range: 1.0×10 -2 ~1.0×10 2 rad / s · Measurement interval: 5 points / decade Absolute value G of complex elastic modulus * (Pa) common logarithm logG * Plot the phase angle δ against logG, and the value of δ (degree) at the point corresponding to logG * = 5.0 was taken as δ (G * = 0.1 MPa). When there is no point corresponding to logG * = 5.0 among the measurement points, the δ value at logG * = 5.0 was obtained by linear interpolation using two points around logG * = 5.0. Also, when all the measurement points are logG * < 5, the logG * value was obtained by a quadratic curve using the values of three points from the larger side, and logG *The δ value at = 5.0 was obtained by extrapolation.

[0090] (2) Activation energy of flow The sample was placed in a heating press mold with a thickness of 1.0 mm, preheated in a hot press machine with a surface temperature of 180 °C for 5 minutes, and then the residual gas in the molten resin was degassed by repeating pressurization and depressurization. Further, it was pressurized at 4.9 MPa and held for 5 minutes. Then, it was transferred to a press machine with a surface temperature of 25 °C and cooled by holding at a pressure of 4.9 MPa for 3 minutes to produce a press plate made of a sample with a thickness of about 1.0 mm. A sample obtained by processing the press plate made of the sample into a 25 mm diameter circle was used, and a complex viscosity was measured under the following conditions using an MCR type rotary rheometer manufactured by Anton Paar as a measuring device for dynamic viscoelastic properties in a nitrogen atmosphere. · Plate: φ25 mm (diameter) parallel plate · Temperature: 140, 160, 180 °C · Strain: 10% · Measurement angular frequency range: 1.0×10 -2 ~1.0×10 2 rad / s · Measurement interval: 5 points / decade Taking 160 °C as the reference temperature, the storage modulus G' and loss modulus G'' under three temperature conditions were superimposed according to the principle of time-temperature superposition to obtain the shift factor a T This shift factor was plotted against the reciprocal of the absolute temperature, and the activation energy of flow Ea was calculated from the slope.

[0091] (3) Measurement of weight average molecular weight (Mw) and molecular weight distribution parameter (Mw / Mn) The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC). Also, the molecular weight distribution parameter (Mw / Mn) was calculated by obtaining the number average molecular weight (Mn) by gel permeation chromatography (GPC) and then taking the ratio of Mw to Mn, Mw / Mn. The measurement was carried out according to the following procedure and conditions. 1) Pretreatment of the sample When the sample contains a carboxylic acid group, methyl esterification treatment was performed using diazomethane or trimethylsilyl (TMS) diazomethane, and the one in which the carboxylic acid group was converted to an ester was used for measurement. When the sample contains a carboxylate group, acid treatment was performed to denature the carboxylate group into a carboxylic acid group, and then the above esterification treatment was performed and used for measurement. 2) Preparation of sample solution 3 mg of the sample and 3 mL of o-dichlorobenzene were weighed into a 4 mL vial, and the vial was capped with a screw cap and a Teflon (registered trademark) septum. 3) Measurement Two high-temperature GPC columns HT-806M manufactured by Resonac were connected to the GPC-IR manufactured by Polymer Char, o-dichlorobenzene was used as the eluent, and the measurement was carried out at a temperature of 145 °C and a flow rate of 1.0 mL / min. 4) Calibration curve The calibration of the column was carried out by measuring monodisperse polystyrene Showdex Standard SM-105 (solutions of 0.05 mg / ml each of S-3210, S-1570, S-607, S-298, S-129, S-49, S-17, S-6.3, S-3.3, S-1.2), n-eicosane and n-tetracosane under the same conditions as above, and the elution time and the logarithm of the molecular weight were approximated by a quartic equation. The following equation was used for the conversion between polystyrene molecular weight (MPS) and polyethylene molecular weight (MPE). MPE = 0.468 × MPS

[0092] (4) Melt flow rate (MFR) As described above, the MFR of the copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms was measured in accordance with JIS-K6922-2:2018 (190 °C, 21.18 N load).

[0093] (5) Melting point and crystallinity The melting point is indicated by the peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). For the measurement, a DSC (DSC7020) manufactured by SII NanoTechnology Inc. was used and carried out under the following measurement conditions. Approximately 5.0 mg of the sample was packed into an aluminum pan, heated to 200°C at a rate of 10°C / min, held at 200°C for 5 minutes, and then cooled to 30°C at a rate of 10°C / min. After holding at 30°C for 5 minutes, when heating up again at a rate of 10°C / min, the maximum peak temperature in the absorption curve was defined as the melting point Tm, the heat of fusion (ΔH) was determined from the melting endothermic peak area, and the crystallinity (%) was determined by dividing the heat of fusion by the heat of fusion of the perfect crystal of high-density polyethylene (HDPE), which is 293 J / g.

[0094] (6) Tensile impact strength 1) Method for preparing a tensile impact strength test sample The sample was placed in a heating press mold with a thickness of 1 mm, preheated in a hot press machine with a surface temperature of 180°C for 5 minutes, and then the sample was melted and the residual gas in the sample was degassed by repeating pressurization and depressurization. Further, it was pressurized at 4.9 MPa and held for 5 minutes. Then, while applying a pressure of 4.9 MPa, it was gradually cooled at a rate of 10°C / min. When the temperature dropped to near room temperature, the molded plate was taken out of the mold. The obtained molded plate was conditioned for 48 hours or more in an environment with a temperature of 23 ± 2°C and a humidity of 50 ± 5°C. A test piece with the shape of ASTM D1822 Type-S was punched out from the conditioned press plate to obtain a tensile impact strength test sample.

[0095] 2) Tensile impact strength test conditions Using the above test piece, the tensile impact strength was measured with reference to Method B of JIS K 7160-1996. Note that the difference from JIS K 7160-1996 is only the shape of the test piece. For other measurement conditions, etc., the test was carried out in accordance with the method specified in JIS K 7160-1996.

[0096] (7) Measurement of the structural unit amounts of monomers having carboxyl groups and / or dicarboxylic anhydride groups and acyclic monomers and the number of methyl branches per 1,000 carbons 1) When the sample contained a carboxylate group, acid treatment was performed to modify the carboxylate group to a carboxylic acid group before measurement.

[0097] 2) Method for measuring the structural unit amount of a monomer having a carboxyl group and / or a dicarboxylic anhydride group and an acyclic monomer, and the number of methyl branches per 1,000 carbons The structural unit amount of the monomer having a carboxyl group and / or a dicarboxylic anhydride group and the acyclic monomer according to the present invention is 1 Using an H-NMR spectrum, the number of methyl branches per 1,000 carbons is 13 Determined using 13C-NMR. 1 The H-NMR spectrum and 13 The 13C-NMR spectrum was measured by the following method. 200 - 250 mg of the sample was placed in an NMR sample tube with an inner diameter of 10 mmφ together with 2.4 ml of o-dichlorobenzene / deuterated benzene (C 6 D 5 Br) = 4 / 1 (volume ratio) and hexamethyldisiloxane which is a chemical shift reference substance, purged with nitrogen, sealed, heated and dissolved to form a homogeneous solution for NMR measurement. The NMR measurement was carried out at 120 °C using an AV400M type NMR apparatus manufactured by Bruker BioSpin Co., Ltd. equipped with a 10 mmφ cryoprobe. 1 For H-NMR, the pulse angle was 1°, the pulse interval was 1.8 seconds, and the number of integrations was 1,024 times or more. The chemical shift was set with the peak of the methyl proton of hexamethyldisiloxane as 0.088 ppm, and the chemical shifts of the peaks by other protons were based on this. 13 For 13C-NMR, the pulse angle was 90°, the pulse interval was 51.5 seconds, the number of integrations was 512 times or more, and it was measured by the inverse gate decoupling method. The chemical shift was set with the peak of the methyl carbon of hexamethyldisiloxane as 1.98 ppm, and the chemical shifts of the peaks by other carbons were based on this.

[0098] 1) Pretreatment of the sample When the sample contained a carboxylate group, acid treatment was performed to modify the carboxylate group to a carboxy group, which was then used for measurement. When the sample contained a carboxy group, esterification treatment such as methylation using diazomethane or trimethylsilyl (TMS) diazomethane was appropriately performed.

[0099] 2) Calculation of the amount of structural units derived from monomers having a carboxy group and / or a dicarboxylic anhydride group and acyclic monomers <e tba> The quaternary carbon signal of the t-butyl acrylate group of tBA is detected at 79.6 - 78.8 ppm in the 13C-NMR spectrum. Using these signal intensities, the comonomer amount was calculated from the following equation. 13 The total amount of tBA (mol%) = I(tBA) × 100 / [I(tBA) + I(E)] Here, I(tBA) and I(E) are the amounts represented by the following equations, respectively. I(tBA) = I I(tBA)=I 79.6~78.8 I(E)=(I 180.0~135.0 +I 120.0~5.0 -I(tBA)×7) / 2

[0100] <e maa> The signal of the carbonyl carbon of methacrylic acid (MAA) is detected at 167.9 ppm in the 13C-NMR spectrum. Using these signal intensities, in the same manner as E / tBA, the comonomer amount was calculated from the following formula. 13 MAA content (mol%) = I MAA content (mol%) = I (MAA) × 100 / (I (E) + I (MAA) ) Here, I (MAA) , I (E) are amounts represented by the following formulas, respectively. I (MAA) = I 167.9 I (E) =(I 180.0~136.0 + I 120.0~100.0 + I 55.0~2.0 - I (MAA) × 5) / 2

[0101] When the amount of the structural unit of each monomer is indicated by "<0.1" including an inequality sign, it means that it exists as a constitutional unit in the copolymer but is less than 0.1 mol% considering significant figures.

[0102] 3) Calculation of the number of branches per 1,000 carbons In the copolymer, there are an isolated type in which a branch exists alone in the main chain and a composite type (a face-to-face type in which branches face each other through the main chain, a branched-branch type having a branch in the branched chain, and a chain type). The following are examples of the structure of ethyl branches. In the example of the face-to-face type, R represents an alkyl group.

[0103]

Chemical formula

[0104] The number of branches per 1,000 carbons is obtained by substituting any of the following I(B1), I(B2), and I(B4) into the I(branch) term of the following formula. B1 represents a methyl branch, B2 represents an ethyl branch, and B4 represents a butyl branch. The number of methyl branches is obtained using I(B1), the number of ethyl branches is obtained using I(B2), and the number of butyl branches is obtained using I(B4). Number of branches (per 1,000 carbons) = I(branch) × 1000 / I(total) Here, I(total), I(B1), I(B2), and I(B4) are quantities represented by the following formulas. I(total) = I 180.0~135.0 + I 120.0~5.0 I(B1) = (I 20.0~19.8 + I 33.2~33.1 + I 37.5~37.3 ) / 4 I(B2) = I 8.6~7.6 + I 11.8~10.5 I(B4) = I 14.3~13.7 - I 32.2~32.0 Here, I is the integrated intensity, and the numerical subscript of I indicates the range of chemical shift. For example, I 180.0~135.0 represents the integrated intensity of the C signal detected between 180.0 ppm and 135.0 ppm. 13 The assignment was made with reference to the non-patent documents Macromolecules 1984, 17, 1756 - 1761 and Macromolecules 1979, 12, 41. Note that when each number of branches is indicated by "<0.1" including an inequality sign, it means that it is present as a constitutional unit in the copolymer but is less than 0.1 mol% considering significant figures. Also, not detected means below the detection limit.

[0105] (8) Shrinkage ratio:(8) Shrinkage ratio: In accordance with JIS K 7152-4:2006, using a FANUC ROBOSHOT 2000i-100B injection molding machine, a flat plate with dimensions of 120×120×2 mm was molded with a one-side film gate (gate thickness 0.2 mm) under the conditions of a molding temperature of 190°C and a mold temperature of 40°C. The shrinkage rate was calculated by dividing the measured value by the length of the mold in the flow direction (MD) immediately after molding.

[0106] 〔Preparation of test pieces〕 Standard number: JIS K-7152 (ISO294-1) Molding machine: FANUC ROBOSHOT 2000i-100B injection molding machine Molding machine set temperature: 30, 180, 190, 190, 190°C from below the hopper Mold temperature: 40°C Injection speed: 50 mm / second Holding pressure: 30 MPa Holding time: 10 seconds Mold shape: Flat plate (thickness 2 mm, width 120 mm, length 120 mm)

[0107] (9) Molding property: Filaments were molded from pelletized resin by the following method, and then 3D printed molded articles were formed from the molded filaments.

[0108] 〈Filament molding method〉 Method for producing filaments: The ionomers described in this application were molded by feeding them into a 65 mm single-screw extruder. Depending on the ionomers used, the barrel temperature was set to 40~240°C. When the molten resin came out of the die, it was quenched in a water bath at a quenching temperature of 25°C. The quenched filaments were wound onto a reel while controlling the speed, and the screw rotation speed and take-up speed were adjusted to a diameter of 1.75 mm.

[0109] 〈Method for forming 3D printed molded articles〉 Filaments with a diameter of 1.75 mm were loaded into a Raise3D Pro2 Plus equipped with a 0.5 mm nozzle and molded under the following conditions. Model in use: Raise3D Pro2 Plus Nozzle temperature: 210 °C Lamination pitch: 0.2 mm Modeling speed: 20 mm / s Shape and dimensions of the molded product: Flat plate of 20×100×t = 0.5 mm, cone of φ20 mm, h = 30 mm (i) Flat plate: 20 mm long, 100 mm wide, 0.5 mm thick, filling rate 100% (ii) Right circular cone: Bottom diameter φ20 mm, height 30 mm, filling rate 15%

[0110] (10) Infrared absorption spectrum The sample was melted at 180 °C for 3 minutes and compression molded to produce a film with a thickness of 50 μm. This film was analyzed by Fourier transform infrared spectroscopy to obtain an infrared absorption spectrum. In the obtained infrared absorption spectrum, the peak near 1700 cm−1 derived from the carbonyl group of carboxylic acid (dimer) decreased, and the peak near 1560 cm−1 derived from the carbonyl group of carboxylate increased. It was confirmed that an ionomer with the desired neutralization degree could be produced from the decrease amount of the peak near 1700 cm−1 derived from the carbonyl group of carboxylic acid (dimer). -1 Near the peak near 1560 cm−1 -1 Near the peak near 1700 cm−1 -1 It was confirmed that an ionomer with the desired neutralization degree could be produced from the decrease amount of the peak near 1700 cm−1 derived from the carbonyl group of carboxylic acid (dimer). Product name: FT / IR-6100 manufactured by JASCO Corporation Measurement method: Transmission method Detector: TGS (Triglycine sulfate) Number of integrations: 16 - 512 times Resolution: 4.0 cm−1 -1 Measurement wavelength: 5000 - 500 cm−1 -1

[0111] (11) Tensile modulus A sheet with a thickness of 1 mm was produced by the method (cooling method A) described in JIS K7151 (1995), and a 5B-shaped small test piece described in JIS K7162 (1994) produced by punching this sheet was used to conduct a tensile test under the condition of a temperature of 23 °C in accordance with JIS K7161 (2014), and the tensile elastic modulus was measured. The test speed was set to 10 mm / min.

[0112] <Synthesis of Metal Complex> Synthesis of B-27DM / Ni Complex For the metal complex, according to Synthesis Example 4 described in International Publication No. WO2010 / 050256, ligand B-27DM represented by the following chemical formula was used. According to Example 1 of International Publication No. WO2010 / 050256, using bis-1,5-cyclooctadiene nickel(0) (referred to as Ni(COD)2), a nickel complex in which B-27DM and Ni(COD)2 reacted in a 1:1 ratio was synthesized.

Chemical Formula

[0113] Synthesis of B-423 / Ni Complex For the B-423 / Ni complex, according to Synthesis Example 1 described in JP-A-2019 / 156764, the following 2-bis(2,6-dimethoxyphenyl)phosphano-6-(2,6-diisopropylphenyl)phenol ligand (B-423) was used. According to Example 1 of JP-A-2019 / 156764, using bis(1,5-cyclooctadiene)nickel(0) (referred to as Ni(COD)2), a nickel complex (B-423 / Ni) in which B-423 and Ni(COD)2 reacted in a 1:1 ratio was synthesized.

Chemical Formula

[0114] <(Production Examples 1 to 3): Production of Ionomer Base Resin Precursor> An ethylene / t-butyl acrylate copolymer was produced using a transition metal complex (B-27DM / Ni complex or B-423 / Ni complex). Using the equipment of a high-pressure low-density polyethylene plant having a 5 L autoclave, the production conditions and production results, such as the metal catalyst species, metal catalyst amount, trioctylaluminum (TNOA) amount or triisopropoxyaluminum (Al(OiPr) 3 ) amount, comonomer species, comonomer amount, ethylene partial pressure, polymerization temperature, polymerization time, etc., which were appropriately changed, are shown in Table 1, and the physical properties of the obtained copolymer are shown in Table 3.

[0115]

Table 1

[0116] <(Production Examples 4 to 8): Production of Ionomer Base Resin Precursor> An ethylene / t-butyl acrylate copolymer was produced using a transition metal complex (B-27DM / Ni complex or B-423 / Ni complex). Referring to Production Example 1 or Production Example 3 described in JP-A-2016-79408, the copolymer was produced, and the production conditions and production results, such as the metal catalyst species, metal catalyst amount, trioctylaluminum (TNOA) amount or triisopropoxyaluminum (Al(OiPr) 3 ) amount, toluene amount, comonomer species, comonomer amount, ethylene partial pressure, polymerization temperature, polymerization time, etc., which were appropriately changed, are shown in Table 2, and the physical properties of the obtained copolymer are shown in Table 3. Not detected in the table means below the detection limit.

[0117]

Table 2

[0118]

Table 3

[0119] <(Resins 1 to 8): Production of E / AA Ionomer Base Resin> Internal volume 1.6 m 3 Into an autoclave made of SUS316L with a stirring blade, 100 kg of any one of the copolymers obtained in Production Examples 1 to 8, 2.0 kg of paratoluenesulfonic acid monohydrate, and 173 L of toluene were charged, and the mixture was stirred at 105 °C for 4 hours. 173 L of ion-exchanged water was added, stirred, allowed to stand, and then the aqueous layer was withdrawn. Thereafter, the addition and withdrawal of ion-exchanged water were repeated until the pH of the withdrawn aqueous layer became 5 or more. The remaining solution was charged into a 42 mmφ vent device twin-screw extruder (L / D = 45.5), and the solvent was removed by pulling the vent under vacuum. Further, the resin continuously extruded in the form of strands from the die at the tip of the extruder was cooled in water and cut with a cutter to obtain resin pellets. In the IR spectrum of the obtained resin, the disappearance of the peak near 850 cm -1 derived from the tBu group and the decrease in the peak near 1730 cm -1 derived from the carbonyl group of the ester, and the increase in the peak near 1700 cm -1 derived from the carbonyl group of the carboxylic acid (dimer) were observed. Thereby, the decomposition of the t-Bu ester and the formation of the carboxylic acid were confirmed, and ionomer base resins 1 to 8 were obtained. The physical properties of the obtained resins are shown in Table 4.

[0120] <(Resins 9 to 11): Production of E / MAA ionomer base resins> Starting from ethylene and methyl methacrylate, copolymers of ethylene and methacrylic acid produced by a high-pressure radical process and the same transesterification as in Resin 1 were obtained as ionomer base resins 9 to 11. The physical properties of the obtained resins are shown in Table 4.

[0121]

Table 4

[0122] 〈Examples 1 to 12: Production of ionomers〉 1) Preparation of Na ion supply source To a twin-screw extruder (L / D = 64) with a 26 mmφ vent device made by Shibaura Machine, ethylene / methacrylic acid (MAA) copolymer (brand: Nucrel M1050H, manufactured by Mitsui DuPont Chemical Co., Ltd.) was continuously charged at a blending ratio of 55 wt%, and sodium carbonate was charged at 45 wt%. Under the kneading conditions of a barrel set temperature of 150 °C and a screw rotation speed of 150 rpm, extrusion was carried out while removing the gas and water generated during kneading from the vent part with a vacuum pump. Further, the resin continuously extruded in the form of strands from the die at the tip of the extruder was cooled in water and cut with a cutter to obtain pellets of the Na ion source.

[0123] 2) Preparation of Zn ion source To a twin-screw extruder (L / D = 64) with a 26 mmφ vent device made by Shibaura Machine, ethylene / methacrylic acid (MAA) copolymer (brand: Nucrel M1050H, manufactured by Mitsui DuPont Chemical Co., Ltd.) was continuously charged at a blending ratio of 54.5 wt%, zinc oxide was charged at 45 wt%, and zinc stearate was charged at 0.5 wt%. Under the kneading conditions of a barrel set temperature of 150 °C and a screw rotation speed of 150 rpm, extrusion was carried out while removing the gas and water generated during kneading from the vent part with a vacuum pump. Further, the resin continuously extruded in the form of strands from the die at the tip of the extruder was cooled in water and cut with a cutter to obtain pellets of the Zn ion source.

[0124] 3) Preparation of ionomer To a twin-screw extruder (L / D = 64) with a 26 mmφ vent device made by Shibaura Machine, any one of Resin 1 to Resin 11 and the Na ion source or Zn ion source were continuously charged at a blending ratio to achieve a desired neutralization degree. Under the kneading conditions of a barrel set temperature of 200 °C and a screw rotation speed of 450 rpm, water was injected at a ratio of 4 parts per 100 parts of the charged resin amount while removing the gas and water generated during kneading from the vent part with a vacuum pump, and extrusion was carried out. Further, the resin continuously extruded in the form of strands from the die at the tip of the extruder was cooled in water and cut with a cutter to obtain pellets of the ionomer. In the IR spectrum of the obtained resin, the peak near 1700 cm−1 derived from the carbonyl group of the carboxylic acid (dimer) decreased, and the peak near 1560 cm−1 derived from the carbonyl group of the carboxylate increased. It was confirmed that an ionomer with the desired neutralization degree could be produced from the decrease amount of the peak near 1700 cm−1 derived from the carbonyl group of the carboxylic acid (dimer). The physical properties of the obtained ionomer are shown in Table 5 and Table 6. -1 In the vicinity of, the peak decreased, and the peak near 1560 cm−1 -1 derived from the carbonyl group of the carboxylate increased. The peak near 1700 cm−1 -1 derived from the carbonyl group of the carboxylic acid (dimer). From the decrease amount of the peak near 1700 cm−1, it was confirmed that an ionomer with the desired neutralization degree could be produced. The physical properties of the obtained ionomer are shown in Table 5 and Table 6.

[0125] Description of Comparative Example and Example Samples Example 1: E / AA-based Binary Ionomer Base Resin: Ethylene·Acrylic Acid Copolymer (Acrylic Acid Content 1.1 mol%) Metal Cation Source: Sodium, Neutralization Degree: 90%, MFR: 1.0 g / 10 min (190 °C, 2.16 kg) Example 2: E / MAA-based Binary Ionomer Base Resin: Ethylene·Methacrylic Acid Copolymer (Methacrylic Acid Content 3.5 mol%) Metal Cation Source: Sodium, Neutralization Degree: 50%, MFR: 5.5 g / 10 min (190 °C, 2.16 kg) Example 3: E / AA-based Binary Ionomer Base Resin: Ethylene·Acrylic Acid Copolymer (Acrylic Acid Content 4.7 mol%) Metal Cation Source: Sodium, Neutralization Degree: 60%, MFR: 1.5 g / 10 min (190 °C, 2.16 kg) Example 4: E / AA-based Binary Ionomer Base Resin: Ethylene·Acrylic Acid Copolymer (Acrylic Acid Content 4.7 mol%) Metal Cation Source: Sodium, Neutralization Degree: 80%, MFR: 0.35 g / 10 min (190 °C, 2.16 kg) Example 5: E / MAA-based Binary Ionomer Base Resin: Ethylene·Methacrylic Acid Copolymer (Methacrylic Acid Content 7.5 mol%) Metal cation source: Sodium, neutralization degree: 47%, MFR: 4.5 g / 10 min (190 °C, 2.16 kg) Example 6: E / AA-based binary ionomer Base resin: Ethylene·acrylic acid copolymer (acrylic acid content 8.5 mol%) Metal cation source: Sodium, neutralization degree: 90%, MFR: 0.2 g / 10 min (190 °C, 2.16 kg) Example 7: E / AA-based binary ionomer Base resin: Ethylene·acrylic acid copolymer (acrylic acid content 12.1 mol%) Metal cation source: Sodium, neutralization degree: 10%, MFR: 1.3 / 10 min (190 °C, 2.16 kg) Example 8: E / AA-based binary ionomer Base resin: Ethylene·acrylic acid copolymer (acrylic acid content 12.1 mol%) Metal cation source: Sodium, neutralization degree: 60%, MFR: 2.3 g / 10 min (190 °C, 2.16 kg) Example 9: E / MAA-based binary ionomer Base resin: Ethylene·methacrylic acid copolymer (methacrylic acid content 3.5 mol%) Metal cation source: Zinc, neutralization degree: 17%, MFR: 5.5 g / 10 min (190 °C, 2.16 kg) Example 10: E / AA-based binary ionomer Base resin: Ethylene·acrylic acid copolymer (acrylic acid content 3.2 mol%) Metal cation source: Zinc, neutralization degree: 73%, MFR: 0.15 g / 10 min (190 °C, 2.16 kg) Example 11: E / AA-based binary ionomer Base resin: Ethylene·acrylic acid copolymer (acrylic acid content 5.4 mol%) Metal cation source: Zinc, neutralization degree: 60%, MFR: 0.9 g / 10 min (190 °C, 2.16 kg) Example 12: E / AA-based binary ionomer Base resin: Ethylene·acrylic acid copolymer (acrylic acid content 7.7 mol%) Metal cation source: zinc, neutralization degree: 80%, MFR: 0.12 g / 10 min (190 °C, 2.16 kg)

[0126] Comparative Example 1: E / AA-based binary ionomer Base resin: ethylene-acrylic acid copolymer (acrylic acid content 0.6 mol%) Metal cation source: sodium, neutralization degree: 60%, MFR: 7.1 g / 10 min (190 °C, 2.16 kg) Comparative Example 2: E / AA-based binary ionomer Base resin: ethylene-acrylic acid copolymer (acrylic acid content 1.1 mol%) Metal cation source: sodium, neutralization degree: 30%, MFR: 13 g / 10 min (190 °C, 2.16 kg) Comparative Example 3: E / AA-based binary ionomer Base resin: ethylene-acrylic acid copolymer (acrylic acid content 12.1 mol%) Metal cation source: sodium, neutralization degree: 90%, MFR: 0.02 g / 10 min (190 °C, 2.16 kg)

[0127]

Table 5

[0128]

Table 6

[0129] The evaluation criteria in Table 6 will be explained. 1) Flexibility Flexibility can be indicated by the value of the tensile elastic modulus, and the smaller the value, the better the flexibility. 2) Impact strength Impact strength is indicated by the tensile impact strength, and the higher the value, the better the impact strength. 3) Moldability i) Fluidity When the melt flow rate is 0.1 g / 10 min or more, the fluidity is sufficient. When it is less than 0.1 g / 10 min, the fluidity is poor, and thus clogging etc. is likely to occur. 〇: The melt flow rate is 0.1 g / 10 min or more. ×: The melt flow rate is less than 0.1 g / 10 min. ii) Warpage The molded product (flat plate of 20×100×t = 0.5 mm, filling rate 100%) molded by the above molding method was observed, and the occurrence situation of warpage was evaluated. When the fluidity was poor and molding was impossible, it was regarded as non - moldable. The warpage referred to in the present application means a state in which a part on either the long - side or short - side of the flat plate floats from the surface of the flat stone plate when the flat plate molded on the flat stone plate is placed. 〇: The molded product is not warped and can be molded. ×: Warpage of the molded product can be visually confirmed. iii) Sag The molded product (right - circular cone of φ20 mm and height 30 mm, filling rate 100%) molded by the following method was observed, and the appearance was evaluated. When the fluidity was poor and molding was impossible, it was regarded as non - moldable. 〇: The laminated surface forms layers without melting to the tip. ×: Molten resin is laminated on a layer where the resin is not sufficiently solidified, and the shape cannot be maintained due to its own weight, resulting in poor molding. When the evaluations in the above i) - iii) are 〇, the moldability is considered good.

[0130] <Results and Discussions of Examples and Comparative Examples> Examples 1 - 12 satisfy the constituent requirements related to the present invention, and are 3D printer resins having excellent moldability, flexibility, and impact resistance of the molded product. As a factor for no sagging, although the carboxylic acid and metal ions in the base resin do not form a crosslinked structure in the molten state and the viscosity is low, it is considered that as the temperature decreases, the molecular momentum decreases and at the same time pseudo-crosslinking forms, resulting in a large increase in viscosity due to the temperature drop. On the other hand, regarding the occurrence of warping, the pseudo-crosslinking of carboxylic acid and metal ions with carboxylic acid in the base resin inhibits crystal formation, and it is considered that warping is suppressed because the volume change between the molten state and after cooling becomes small. Also, it is considered that by forming pseudo-crosslinking, the molecular structure becomes network-like and the impact strength increases. On the other hand, in Comparative Example 1, pseudo-crosslinking is formed by the amount of carboxylic acid and metal ions in the base resin, but since there is little carboxylic acid in the base resin, crystals are easily formed and warping occurs. Also, since the amount of carboxylic acid in the base resin is small, even when the neutralization degree is high, sufficient pseudo-crosslinking is not formed and sagging occurs. Regarding Comparative Example 2, since the content of the metal-containing carboxylate base is low and the pseudo-crosslinking is insufficient, crystals are easily formed and warping occurs. Regarding Comparative Example 3, since the amount of pseudo-crosslinking formed by the carboxylic acid and metal ions contained in the base resin increases, the melt flow rate becomes very low and the fluidity deteriorates, resulting in clogging of the nozzle and causing molding defects.< / e> < / e>

Claims

1. A resin composition for 3D printers, comprising: a copolymer (P) containing, as essential constituent units, structural units (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and structural units (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group; at least a portion of the carboxyl groups and / or dicarboxylic anhydride groups in the copolymer (P) are converted to a metal-containing carboxylate containing at least one type of metal ion; an ionomer having a neutralization amount of 0.4 to 10 mol%; and optionally a thermoplastic resin not falling under the category of the ionomer, the amount of the ionomer being 50 mass% or more relative to the entire resin composition.

2. The resin composition for 3D printers according to claim 1, wherein the copolymer (P) contains 1.0 to 20.0 mol% of the structural unit (B) in the copolymer.

3. The ionomer according to claim 1, characterized in that at least a portion of the carboxyl groups and / or dicarboxylic anhydride groups of the copolymer (P) are neutralized by 1% to 90% with a metal-containing carboxylate containing at least one type of metal ion. The resin composition for 3D printers according to claim 1.

4. The resin composition for 3D printers according to claim 1, wherein the structural unit (A) is a structural unit derived from ethylene.

5. The resin composition for 3D printers according to claim 1, wherein the metal ion is at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table.

6. The resin composition for 3D printers according to claim 1, wherein the ionomer has a flow activation energy of 40 kJ / mol or more.

7. The resin composition for 3D printers according to claim 1, characterized in that the crystallinity of the ionomer is 50% or less.

8. The resin composition for 3D printers according to claim 1, wherein the melting point of the ionomer is in the range of 60 ° C. to 130 ° C.

9. A 3D printed product formed by depositing one or more lines of molten resin using the resin composition for 3D printers according to any one of claims 1 to 8.

10. A method for producing a 3D printed object, comprising the step of depositing the resin composition for a 3D printer according to any one of claims 1 to 8 in a plurality of layers using a 3D printer to form a shaped object.

Images