JP2020002201A - Method for manufacturing molded body - Google Patents

Abstract

To provide a method for manufacturing a molded body which exhibits excellent well-balanced performance in mechanical strength, adhesion to metal and appearance uniformity than a conventional manufacture method using (meth)acrylate metal.SOLUTION: A method for manufacturing a molded body includes: a step of kneading salt containing anion represented by formula (1) and metal-containing cation and/or a compound generating the anion and a compound generating the metal-containing cation, and a composition containing a resin generating an activity point crosslinkable in the structure by radical; a step of generating the radical in the composition after the kneading step and subjecting the composition to crosslinking treatment; and a step of molding the composition before crosslinking treatment and/or the crosslinked body after crosslinking treatment.SELECTED DRAWING: None

Description

The present invention relates to a method for manufacturing a molded article. More specifically, it is a method for producing a resin molded body having a crosslinked structure by metal ion bonding, and the molded body obtained exhibits excellent performance in a well-balanced manner in mechanical strength, adhesion to metal and appearance uniformity. The present invention relates to a method for manufacturing a molded article.

By crosslinking raw resin such as raw rubber or thermoplastic resin, non-thermoplastic resin such as rubber or plastic excellent in mechanical strength, heat resistance, durability, oil resistance and the like can be obtained. As a method for obtaining such rubber, plastic, or the like, for example, for a resin that can be crosslinked with a radical, a method of generating a radical and crosslinking with a polyfunctional vinyl compound is known. Regarding such a method, Patent Literature 1 discloses that a specific hydrogenated nitrile rubber is crosslinked using a polyfunctional (meth) acrylate to produce a highly durable rubber having improved mechanical strength, oil resistance, and abrasion resistance. A method for doing so is disclosed. Patent Literature 2 discloses a method of manufacturing a fluororubber molded article by cross-linking an unvulcanized fluororubber compound using triallyl isocyanurate by irradiation with active energy rays and heating. Patent Literature 3 discloses a method of manufacturing an insulated power cable in which an ethylene / polar monomer copolymer is crosslinked using triallyl isocyanurate to increase the gel fraction and improve insulation performance. Patent Document 4 discloses a method of forming an insulator layer of a power cable by extrusion-coating a polyolefin with a compound having two or more maleimide groups, followed by crosslinking.
Further, in order to improve the mechanical strength, oil resistance, adhesion, and the like of the obtained non-thermoplastic resin, a technique of cross-linking the raw resin using an unsaturated metal salt among polyfunctional vinyl compounds has been developed. For example, Patent Document 5 discloses a method for improving heat resistance and durability by crosslinking natural rubber, butadiene rubber, SBR, and EPDM using zinc (meth) acrylate. Patent Literature 6 discloses a method of improving adhesiveness by cross-linking hard-to-adhesive silicone rubber using zinc (meth) acrylate. It has been shown that it is necessary to crosslink in combination with zinc (meth) acrylate and a polyfunctional radical reactive compound. Patent Document 7 discloses a method of improving hardness by crosslinking butadiene rubber using zinc acrylate and zinc stearate. However, in order to obtain a sufficiently good dispersion state, coating with a rubber for coating is disclosed. It is indicated that it is necessary to mix the prepared zinc acrylate and zinc stearate. Non-Patent Document 1 discloses the main features and uses of various raw rubbers and the purposes and types of various rubber compounding agents, and furthermore, zinc stearate or the like blooms on the surface of the vulcanized rubber left for a while after vulcanization. Is disclosed.
Meanwhile, Patent Documents 8 and 9 disclose a diene-based carboxylate ion having a specific structure, a composition containing the same, and a cured product thereof.

JP 2006-131700 A JP 2004-160902 A JP 2006-36876 A JP 2006-66110 A JP 2011-57776 A JP-A-2006-79347 JP 2005-179522 A JP 2012-107208 A JP 2013-231164 A

Journal of The Rubber Society of Japan, Vol. 88, No. 6, 2015, pp 192-197

As described above, as a method for producing a molded article, for example, a method of cross-linking various resins using a (meth) acrylic acid metal salt has been disclosed. However, in a conventional production method using a (meth) acrylic acid metal salt, The balance of mechanical strength, adhesion to metal and uniformity of appearance of the obtained molded product was not sufficient.

The present invention has been made in view of the above-mentioned situation, and the obtained molded product has more mechanical strength, adhesion to metal, and uniform appearance than conventional production methods using a metal (meth) acrylate. It is an object of the present invention to provide a method for producing a molded body exhibiting excellent performance in a well-balanced manner.

The present inventors have conducted various studies on the method for producing a molded article, and found that the method includes a salt containing an anion having a specific structure and a metal-containing cation and / or a compound capable of forming such a salt and a resin capable of being cross-linked by radicals. Performing a step of kneading the composition, a step of generating a radical in the composition after the kneading step to perform a crosslinking treatment, and a step of molding the composition before the crosslinking treatment and / or the crosslinked body after the crosslinking treatment As a result, it has been found that the obtained molded body exhibits excellent performance in a well-balanced manner in mechanical strength, adhesion to metal, and appearance uniformity as compared with the conventional production method using a metal (meth) acrylate.
Specifically, the salt having the above specific structure and / or the compound that forms the salt is easily mixed with the resin in the composition and has high reactivity (polymerization activity), so that the resin is efficiently crosslinked. I can do it. Further, by cross-linking such a composition, the salt undergoes cyclization polymerization and becomes a compound having a ring structure and a metal ion bond in a cross-linked structure. It has been found that both the adhesiveness and the uniformity of the appearance exhibit excellent performance in a well-balanced manner. Thus, the present inventors have conceived that the above-mentioned problems can be solved successfully, and have reached the present invention.

That is, the present invention provides the following formula (1):

(In the formula, R represents a hydrogen atom or a methyl group. X ¹ , Y ¹ and Z ¹ are the same or different and each represents a methylene group which may have a substituent or an oxygen atom. However, at least one of X ¹ , Y ^1, and Z ¹ is an oxygen atom, and a bond of an oxygen atom—a carbon atom—an oxygen atom represented by a dotted line and a solid line corresponds to two bonds included in the bond. A carbon atom-oxygen atom bond is equivalent, and the entire bond of the oxygen atom-carbon atom-oxygen atom is a monovalent anion.) And a metal-containing cation. And / or a step of kneading a composition containing a compound that generates the anion and a compound that generates the metal-containing cation, and a resin that generates a crosslinkable active site in the structure by a radical; Boombox in the composition A step of performing crosslinking treatment to generate a method for producing a molded body and a step of molding the composition prior to crosslinking treatment and / or crosslinking treatment after crosslinked.

The present invention also provides the following formula (1):

(In the formula, R represents a hydrogen atom or a methyl group. X ¹ , Y ¹ and Z ¹ are the same or different and each represents a methylene group which may have a substituent or an oxygen atom. However, at least one of X ¹ , Y ^1, and Z ¹ is an oxygen atom, and a bond of an oxygen atom—a carbon atom—an oxygen atom represented by a dotted line and a solid line corresponds to two bonds included in the bond. A carbon atom-oxygen atom bond is equivalent, and the entire bond of the oxygen atom-carbon atom-oxygen atom is a monovalent anion.) And a metal-containing cation. And / or a composition comprising a compound that generates the anion and a compound that generates the metal-containing cation, and a resin that generates a crosslinkable active site in the structure by a radical.

Further, the present invention provides the following formula (2) and / or formula (3);

(In the formula, R represents a hydrogen atom or a methyl group. X ¹ , Y ¹ and Z ¹ are the same or different and each represents a methylene group which may have a substituent or an oxygen atom. However, at least one of X ¹ , Y ^1, and Z ¹ is an oxygen atom, and M represents a metal-containing cation.) And an activity capable of being cross-linked into the structure by a radical. It is also a molded article that has a point, and has a structural unit derived from a resin having no structural unit represented by Formulas (2) and (3).

The method for producing a molded article of the present invention includes the above-described structure, and the obtained molded article exhibits excellent performance in a well-balanced manner in mechanical strength, adhesion to metal, and appearance uniformity, and is suitable for various uses. It can be suitably used.

FIG. 1 is a conceptual diagram schematically showing a mechanism of cyclopolymerization of an anion represented by the formula (1).

Hereinafter, preferred embodiments of the present invention will be specifically described, but the present invention is not limited to only the following description, and can be appropriately modified and applied without departing from the gist of the present invention. It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below also corresponds to a preferred embodiment of the present invention.

1. Method for Producing a Molded Article The method for producing a molded article of the present invention comprises a salt containing an anion represented by the above formula (1) and a metal-containing cation (hereinafter also referred to as a diene carboxylate), and / or Alternatively, a composition comprising a compound that generates the anion and a compound that generates the metal-containing cation, and a resin that generates a crosslinkable active site in a structure by a radical (hereinafter, also referred to as a radically crosslinkable resin). , A step of generating a radical in the composition after the kneading step to perform a crosslinking treatment, and a step of molding the composition before the crosslinking treatment and / or the crosslinked body after the crosslinking treatment.
The above molding step may be performed simultaneously with the kneading step or after the kneading step and before the crosslinking treatment step. In this case, the composition before the crosslinking treatment is molded. In addition, the molding step may be performed after the kneading step, simultaneously with the molding step and the crosslinking treatment step, or after the crosslinking treatment step. When the molding step and the crosslinking treatment step are performed simultaneously, the composition before the crosslinking treatment and / or the crosslinked body after the crosslinking treatment is molded. When the molding step is performed after the crosslinking treatment step, the crosslinked body after the crosslinking treatment is molded. Will be done.
The method for manufacturing a molded article of the present invention may include other steps as long as these steps are included.

≪Kneading process≫
In the kneading step, a composition comprising a diene-based carboxylate and / or a compound that generates an anion and a compound that generates a metal-containing cation represented by Formula (1), and a radically crosslinkable resin ( There is no particular limitation as long as the components in the raw material composition are mixed and dispersed while suppressing the crosslinking reaction.
The kneading step may include a diene carboxylate in the composition, or may include a compound that generates an anion represented by the formula (1) and a compound that generates a metal-containing cation. When a compound containing an anion-forming compound and a metal-containing cation is contained, an anion represented by the formula (1) and a metal-containing cation represented by the formula (1) during the kneading, molding, and crosslinking treatment steps for the composition containing these compounds. Will occur. That is, even when the composition does not contain a diene carboxylate, the anion represented by the formula (1) is obtained during the kneading, molding, and crosslinking treatment steps for the composition containing these compounds. As long as the metal-containing cation and the metal-containing cation are generated, the obtained molded article has a metal cross-linking structure derived from the anion represented by the formula (1) and the metal-containing cation, so that the effects of the present invention are exhibited. When the composition contains a compound that generates an anion and a compound that generates a metal-containing cation, among the kneading, molding, and crosslinking treatment steps, the anion and the metal-containing cation represented by the formula (1) during the kneading step. Preferably occurs.

In the following, the essential components (the diene carboxylate and / or the compound that generates the anion and the compound that generates the metal-containing cation represented by the formula (1)) contained in the raw material composition in the kneading step, and the radical The crosslinkable resin) and optional components (other components other than the diene carboxylate and the radically crosslinkable resin) will be described.

<Diene carboxylate, and / or compound that generates the anion and compound that generates the metal-containing cation>
(1) Anion in diene carboxylate (diene carboxylate anion)
The anion in the diene carboxylate of the present application is a 1,6-diene-2-carboxylate anion represented by the formula (1). Examples of the substituent of the methylene group which may have a substituent of the formula (1) include an alkyl group having 1 to 6 carbon atoms. The substituent is preferably a methyl group. It is preferable that the methylene group has no substituent.
As shown in the above formula (1), the diene-based carboxylate anion has a structure in which the entire bond of oxygen atom-carbon atom-oxygen atom is a monovalent anion.

The diene carboxylate anion may have a plurality of different structures as a coordination structure, or may be a mixture of a plurality of coordination structures.
Examples of the coordination structure include, but are not limited to, a monodentate ligand, a bidentate ligand, and a bridging ligand. Further, with the same chemical formula, those having different coordination structures may be treated as the same.
For example, the diene carboxylate anion may be compounded with other anions other than the diene carboxylate anion represented by (1).

Since the diene-based carboxylate anion can undergo cyclization polymerization as shown in FIG. 1, it has extremely excellent polymerizability regardless of the ionization state.
Therefore, it is possible to efficiently modify a wide variety of resins, and since the obtained molded article has a ring structure, it has excellent mechanical strength and adhesion due to the appropriate flexibility of the ring structure. It becomes.

The diene-based carboxylate anion is preferably a case where X ¹ = Z ¹ = methylene group and Y ¹ = oxygen atom, and the diene-based carboxylate anion is represented by the following formula (4): This is the case of an anion of ((meth) allyloxymethyl) acrylic acid. That is, the diene carboxylate is preferably in the form of 2-((meth) allyloxymethyl) acrylate.

In the formula, R represents a hydrogen atom or a methyl group. Oxygen atom-carbon atom-oxygen atom bond represented by a dotted line and a solid line is equivalent to two carbon atom-oxygen atom bonds contained in the bond, and the entire oxygen atom-carbon atom-oxygen bond It represents that it is a monovalent anion.

(2) Counter cation in diene carboxylate The cation in the diene carboxylate of the present application (hereinafter, also referred to as counter cation) is not particularly limited as long as it is a metal-containing cation. It may be an atomic group containing both, or may be an atomic group consisting of a metal atom or only a metal atom. When the counter cation is an atomic group including both a metal atom and a non-metal atom, the entire atomic group including the metal atom and the non-metal atom may be regarded as one cation, or the metal atom or the metal atom may be regarded as one cation. The atomic group consisting only of the cations may be a cation, and the other portions may be regarded as anions. (For example, [ZrO] ²⁺ is Zr ⁴⁺ and O ²⁻ , [(C ₂ H ₅ O) Al] ²⁺ is Al ³⁺ and C ₂ H ₅ O ⁻ , [(n−C ₄ H ₉ ) ₂ Sn—O _{-Sn (n-C 4 H 9} ) 2] 2+ 2 pieces ^{Sn 4+} and ^{O 2-} and _n-C 4 _{H 9} ^- 2 pieces).

Since the counter cation is a cation which is a metal atom or an atomic group containing a metal atom, the counter cation is not only a property derived from ionic bonding but also derived from the metal itself in a molded product having a structure derived from the diene carboxylate. Properties may also be imparted. The counter cation in the diene carboxylate is preferably a metal ion.

Examples of the metal contained in the counter cation include alkali metals, alkaline earth metals, typical metals of Groups 12 to 16 of the periodic table, and transition metals of Groups 3 to 11 of the periodic table. From the viewpoint of crosslinkability, a metal capable of having a valence of 2 or more is preferable. In consideration of availability of metals and ease of synthesis, more preferably, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanoid, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese , Iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, gallium, indium, silicon, germanium, tin, lead, antimony, and bismuth. Transition metal elements such as chromium, manganese, iron, and cobalt are often colored, so if you do not want to be colored as much as possible, magnesium, calcium, strontium, barium, zinc, aluminum, gallium, indium, germanium, tin, lead, Typical metals such as antimony and bismuth, Group 3 transition metals such as yttrium and lanthanum, and Group 4 transition metals such as titanium and zirconium can be more preferably used. Particularly preferred are typical metals such as magnesium, calcium, strontium, barium, zinc, aluminum, gallium, indium, germanium, tin, lead, antimony, bismuth, and more preferably magnesium, calcium, from the viewpoint of biosafety. Zinc and aluminum, most preferably zinc.

(3) Diene carboxylate The diene carboxylate of the present invention contains the above-mentioned carboxylate anion and the above-mentioned counter cation.

The diene-based carboxylate is, like a normal carboxylate anion, in a highly polar solvent such as water when it is solvated with solvent molecules and ionized (so-called electrolyte solution), In a polar solvent or poor solvent, or in the absence of a solvent, it exists in the form of a salt bonded to a counter cation by ionic bonding. In the above raw material composition, an equivalent amount of a diene carboxylate anion and a metal-containing cation are contained, and if the whole is electrically neutral, the diene carboxylate anion and the counter cation are bound. Or in an ionized state.

In the diene-based carboxylate, to confirm that the anion portion is present in the state of an anion, it can be confirmed by a method similar to a method applied to the identification of a normal carboxylate anion. Identification and analysis using various chromatography techniques are preferred.

When the diene-based carboxylate anion contains an electrolyte solution in the raw material composition, it may be in an ionized state in the electrolyte solution. Tends to exist in a state.

In addition, the diene-based carboxylate may contain a plurality of different coordination structures as long as the diene-based carboxylate anion is a salt represented by the same chemical formula.
The diene carboxylate may include a structure other than the diene carboxylate anion and the counter cation described above, and at least one of the valences of the counter cation is occupied by the diene carboxylate anion. And the remaining valences may be occupied by other anions other than the diene-based carboxylic acid, neutral ligands, or the like.
Further, depending on the valency of the counter cation and the possible coordination number, it may contain only one kind, or may have plural kinds or plural kinds of different kinds. Other anions include, for example, oxide ions (O ²⁻ ), halogen ions, hydroxide ions, alkoxide ions, carboxylate anions other than diene carboxylate anions, acetylacetonate ions, carbonate ions, Examples thereof include hydrogen carbonate ion, nitrate ion, nitrite ion, sulfate ion, sulfite ion, hydrogen sulfite ion, phosphate ion, silicate ion, and borate ion. Examples of the neutral molecular ligand include water, alcohols, ammonia, amines, phosphines, β-keto esters, cyclopentadiene, and the like.
As described above, the diene-based carboxylate is represented by a chemical formula representing a component (a carboxylate anion, a counter cation, other anions, a neutron molecule type ligand, etc.) constituting the diene-based carboxylate.
The properties of the diene carboxylate are not particularly limited, and may be liquid or solid.For example, a kneading apparatus and a condition are selected according to the properties of the diene carboxylate, and components such as a resin. It is preferable to adapt.
When the diene carboxylate anion contains many organic groups, it tends to be liquid at normal temperature. In particular, in the structure where the diene carboxylate anion is represented by the formula (1), X ¹ , Z ¹ Are the same or different and may be substituted with a methylene group and Y ¹ = oxygen atom, they tend to be liquid at room temperature.

Further, as described above, since the diene carboxylate has a metal atom or an atomic group containing a metal atom as a counter cation, the property derived from the metal ion bond between the diene carboxylate anion and the metal ion in the salt. Based on the above, the obtained molded body is excellent in mechanical strength and adhesion.

As a preferred combination of the diene carboxylate anion and the counter cation in the diene carboxylate of the present invention, the anion of 2-((meth) allyloxymethyl) acrylic acid represented by the formula (4) and a metal It is a combination with ions.

Hereinafter, preferred embodiments of the diene carboxylate will be described with reference to examples. Here, as described above, the diene-based carboxylate anion is preferably 2-((meth) allyloxymethyl) acrylate anion, and 2- (allyloxymethyl) acrylate anion (hereinafter, AOMA ion). Is the most preferred form. Therefore, in the following preferred embodiments of the diene-based carboxylate, only the case where the diene-based carboxylate anion contains an AOMA ion is listed. However, the present invention is not limited to such an example, and other diene-based carboxylate anions may be used. It does not deny the case where ions are contained or the case where plural kinds of diene carboxylate anions are contained. In the following examples, (CH ₃ ) ₄ N represents a tetramethylammonium ion and (Ph) ₄ P tetraphenylphosphonium ion, and the positive and negative and valence of each ion are omitted.

Examples of AOMA ions and only one kind of counter cation include Li (AOMA), Na (AOMA), K (AOMA), (CH ₃ ) ₄ N (AOMA), and (Ph) ₄ P (AOMA). , Mg (AOMA) ₂ , Ca (AOMA) ₂ , Sr (AOMA) ₂ , Ba (AOMA) ₂ , Y (AOMA) ₃ , La (AOMA) ₃ , Ti (AOMA) ₄ , Zr (AOMA) ₄ , Cr (AOMA) ₃ , Mn (AOMA) ₂ , Fe (AOMA) ₃ , Co (AOMA) ₂ , Ni (AOMA) ₂ , Cu (AOMA) ₂ , Ag (AOMA), Zn (AOMA) ₂ , Al (AOMA) ₃ , In (AOMA) ₃ and Bi (AOMA) ₃ .

Examples of the complex with an oxide anion other than the AOMA ion as the anion include Zr (O) (AOMA) ₂ and V (O) (AOMA) ₂ .

Examples of anions combined with a carboxylate anion such as an acetate anion (hereinafter, Ac), an acrylate anion (hereinafter, AA), and a methacrylate anion (hereinafter, MAA) other than the AOMA ion as an anion. Is
Ca (AOMA) ₁ (Ac) ₁ , Ba (AOMA) ₁ (AA) ₁ , Zr (AOMA) ₂ (MAA) ₂ , Zn (AOMA) ₁ (AA) ₁ , In (AOMA) ₂ (MAA) _1, etc. Is mentioned.

As an example in which an anion is combined with a carbon anion such as n-butyl anion (hereinafter, n-C ₄ H ₉ ) in addition to the AOMA ion, (n-C ₄ H ₉ ) ₂ Sn (AOMA) ₂ , (nC ₄ H ₉ ) ₂ Pb (AOMA) _{2 and the} like.

In addition to the AOMA ion as an anion, examples of the complex with an oxide anion and a carbon anion include (CH ₃ ) ₄ Sn ₂ (O) (AOMA) _{2 and the} like.

Examples of the combination of a plurality of types as counter cations include (La) ₁ (Cu) ₂ (AOMA) ₇ , ((C ₂ H ₅ ) ₃ NH) ₁ (Ag) ₁ (AOMA) _{2, and the} like. No.
Examples of anionic ligands other than carboxylic acids include hydroxide ions, alkoxide ions, and halogen ions.
(Ph) ₂ Sn (OH) ₁ (AOMA) ₁ , (nC ₄ H ₉ O) ₂ Ti (AOMA) ₂ , Y (Cl) (AOMA) _{2 and the} like.
Examples of water, methanol and 2,2′-bipyridine (hereinafter bpy) coordinated as neutral ligands include (H ₂ O) ₂ Zn (AOMA) ₂ and (H ₂ O) ₁ (CH ₃ OH) ₁ Zn (AOMA) ₂ , (bpy) ₂ Sm (AOMA) _{3 and the} like.
In addition, those which can be generally used as a solvent such as water, methanol, diethyl ether, tetrahydrofuran, etc. may be contained in a salt as a neutral molecule type ligand, or may be simply a mixture of a salt and a residual solvent. Is not distinguished.

(4) Method for producing diene-based carboxylate: As the method for producing the diene-based carboxylate, (i) diene-based carboxylic acid or anhydride of diene-based carboxylic acid is mixed with a basic substance and / or an amphoteric substance. A reaction method (hereinafter referred to as a direct method), (ii) a diene-based carboxylic acid ester or a diene-based carboxylic acid nitrile is hydrolyzed with a basic substance to form a diene-based carboxylate, and then, if necessary, another cation. (Hereinafter referred to as a double decomposition method). Further, when the diene carboxylate is produced in the diene carboxylate electrolyte solution, an ionized diene carboxylate anion can be obtained. When operations such as exchange and extraction are performed, a state of a diene carboxylate can be obtained, and the diene carboxylate may be obtained in an ionized state or in a non-ionized state. .
In the above-mentioned production method, the basic substance refers to a substance capable of generating hydroxide ions by reacting with water (which may be heated). Examples of the basic substance include organic bases such as ammonia and amines. A simple metal, a metal oxide, a metal hydroxide and a metal alkoxide are exemplified. The amphoteric substance refers to a substance that can react with both an acid and a base, and includes, for example, a simple substance of a metal containing elements such as aluminum, zinc, tin, and lead, a metal oxide, a metal hydroxide, and a metal alkoxide. .
The metal contained in the basic substance and the amphoteric substance is preferably a metal contained in the above-mentioned counter cation.
Regarding the points other than the above of the direct method and the metathesis method, the method described in Patent Document 8 can be referred to.

(5) Compound for generating anion represented by formula (1) and compound for generating metal-containing cation The raw material composition in the kneading step comprises a compound capable of generating an anion represented by formula (1) and a metal-containing cation. It may contain a compound that generates a cation.
The compound that generates the anion represented by the formula (1) is not particularly limited as long as the compound generates the anion during the kneading, molding, and crosslinking treatment steps. Protonated acids and the like can be mentioned.
The compound that generates the metal-containing cation is not particularly limited as long as it generates the cation during the kneading, molding, and crosslinking treatment steps. For example, the compound is represented by the above-described metal-containing cation and Formula (1). Salts containing anions other than anions are exemplified.
Specific examples and preferred examples of the metal-containing cation are as described in the diene carboxylate.
The anion other than the anion represented by the formula (1) is not particularly limited, but may be an oxide ion (O ²⁻ ), a halogen ion, a hydroxide ion, an alkoxide ion, or a carboxylic acid other than a diene carboxylate anion. Acid anion, acetylacetonate ion, carbonate ion, hydrogen carbonate ion, nitrate ion, nitrite ion, sulfate ion, sulfite ion, hydrogen sulfite ion, phosphate ion, silicate ion, borate ion, etc. .
The anion other than the anion represented by the formula (1) is preferably an oxide ion, a hydroxide ion, a carboxylate anion other than the diene carboxylate anion, a carbonate ion, or a hydrogen carbonate ion. The compound that generates a metal-containing cation is preferably a metal oxide, a metal hydroxide, a metal alkoxide, a metal carboxylate other than a diene carboxylate anion, a carbonate, or a hydrogen carbonate, and more preferably a metal oxide. And a metal hydroxide, particularly preferably zinc oxide.

(6) The content ratio of the diene carboxylate in the raw material composition and the compound that generates the anion represented by the formula (1) and the compound that generates the metal-containing cation. Diene in the raw material composition in the kneading step. The total content of the system carboxylate, the compound that generates the anion represented by the formula (1), and the compound that generates the metal-containing cation is not particularly limited, but 100% by mass of a radically crosslinkable resin. Is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more. Further, it is preferably at most 70% by mass, more preferably at most 60% by mass, further preferably at most 50% by mass. By setting the content in the above preferable range, the function and effect of the present invention can be more sufficiently exhibited.
When calculating the above ratios, the compounds which generate the anion represented by the formula (1) and the compounds which generate the metal-containing cation are converted into the anion and the metal-containing cation represented by the formula (1). Then, the above ratio is calculated. For example, when 2- (allyloxymethyl) acrylic acid and zinc oxide are contained as the compound for generating the anion represented by the formula (1) and the compound for generating the metal-containing cation, 2- (allyloxymethyl) acrylic is used. The above ratio is calculated as an acid anion and a zinc ion.
Further, the form in which the raw material composition contains a diene carboxylate is a preferred embodiment of the present invention, and the content ratio of the diene carboxylate in the raw material composition is not particularly limited. It is preferably at least 0.5% by mass, more preferably at least 1% by mass, and still more preferably at least 2% by mass, based on 100% by mass of a possible resin. The content is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

<Resin that generates active sites capable of cross-linking in the structure by radicals>
The resin contained in the raw material composition in the kneading step generates a crosslinkable active site in the structure due to radicals, and is crosslinked in the cross-linking step. Examples of the resin include a rubber and a thermoplastic resin (thermoplastic, thermoplastic elastomer), and a resin that can be classified as a rubber or a thermoplastic resin.
The rubber may be an unvulcanized raw rubber or a vulcanized rubber.
The rubber is preferably an unvulcanized raw rubber.

Examples of the raw rubber include those described in JIS K 6397: 2005. Specifically, as a member of the M group (rubber having a polymethylene-type saturated main chain), a rubber-like mixture of ethyl acrylate or other acrylates and a small amount of a monomer capable of vulcanization is used. Copolymer (acrylic rubber: ACM), rubbery copolymer of ethyl acrylate or other acrylates with ethylene (AEM), rubbery copolymer of ethyl acrylate or other acrylates with acrylonitrile Polymer (ANM), chlorinated polyethylene (CM), chlorosulfonated polyethylene (CSM), rubbery copolymer of ethylene and butene (EBM), rubbery copolymer of ethylene and octene (EOM), ethylene Rubber-like copolymer of ethylene and propylene (EPDM), rubber-like copolymer of ethylene and propylene (EPM), ethylene and vinyl acetate Copolymer with ethylene (EVM), rubber copolymer with ethylene tetrafluoride and propylene (FEPM), rubber-like copolymer in which all side chains are fluoro and perfluoroalkyl or perfluoroalkoxy groups (FFKM), rubbery copolymer (FKM) having fluoro and perfluoroalkyl or perfluoroalkoxy groups on the side chain, polyisobutene (IM), rubbery copolymer of acrylonitrile and butadiene having a main chain completely hydrogenated Polymer (NBM), rubbery copolymer of styrene, ethylene and butene (SEBM), rubbery copolymer of styrene, ethylene and propylene (SEPM);

Polychloromethyloxirane (epichlorohydrin rubber; CO), a rubber-like copolymer of ethylene oxide and epichlorohydrin (ECO), and epichlorohydrin include those belonging to the O group (rubber having carbon and oxygen in the main chain). Rubber-like copolymer of hydrin and allyl glycidyl ether (GCO), rubber-like copolymer of ethylene oxide, epichlorohydrin and allyl glycidyl ether (GECO), rubber-like copolymer of propylene oxide and allyl glycidyl ether Coalescence (GPO);

Silicon rubber (FMQ) having a methyl substituent and a fluoro substituent on the polymer chain, a methyl rubber, a vinyl substituent and a fluoro substituent on the polymer chain as members of the Q group (rubber having silicon and oxygen in the main chain). Silicone rubber having a substituent (FVMQ), silicone rubber having a methyl substituent in a polymer chain (polydimethylsiloxane: MQ), silicone rubber having a methyl substituent and a phenyl substituent in a polymer chain (PMQ), polymer chain A silicone rubber having a methyl substituent, a vinyl substituent and a phenyl substituent (PVMQ), a silicone rubber having a methyl substituent and a vinyl substituent in a polymer chain (VMQ);

Acrylate butadiene rubber (ABR), butadiene rubber (BR), chloroprene rubber (CR), epoxidized natural rubber (ENR), and hydrogenated hydrogen are included in the R group (rubber having an unsaturated carbon bond in the main chain). Rubber-like copolymer of acrylonitrile and butadiene (HNBR), isoprene rubber (synthetic natural rubber: IR), rubber-like copolymer of α-methylstyrene and butadiene (MSBR), rubber-like of acrylonitrile, butadiene and isoprene Copolymer (NBIR), rubbery copolymer of acrylonitrile and butadiene (nitrile rubber: NBR), rubbery copolymer of acrylonitrile and isoprene (NIR), natural rubber (NR), norbornene rubber (NOR), Rubbery copolymer of vinylpyridine and butadiene (PBR) Rubbery copolymer of styrene, styrene and butadiene (PSBR), rubbery copolymer of styrene and butadiene (SBR), rubbery copolymer of styrene and butadiene synthesized by emulsion polymerization (E-SBR) ), A rubbery copolymer of styrene and butadiene (S-SBR) synthesized by solution polymerization, a rubbery copolymer of styrene, isoprene and butadiene (SIBR), a carboxylated butadiene rubber (XBR), Carboxylated chloroprene rubber (XCR), rubber-like copolymer of carboxylated acrylonitrile and butadiene (XNBR), rubber-like copolymer of carboxylated styrene and butadiene (XSBR);

As a member of the T group (rubber having carbon, oxygen and sulfur in the main chain), a —CH ₂ —CH ₂ —O—CH ₂ —O—CH ₂ —CH ₂ — group between polysulfide bonds in a polymer chain Or a rubber (OT) having either an R group (R is an aliphatic hydrocarbon) and usually having no —CH ₂ —CH ₂ — group, —CH ₂ —CH ₂ — between polysulfide bonds in a polymer chain. _{O-CH 2 -O-CH 2} -CH 2 - group and normal _-CH 2 -CH ₂ - rubber having a group (other aliphatic groups optionally) (EOT);

As those belonging to the U group (rubber having carbon, oxygen and nitrogen in the main chain), rubbery copolymers of ethylene tetrafluoride, nitrosomethane trifluoride and nitrosoperfluorobutyric acid (AFMU), polyester urethane (AU) ), Polyether urethane (EU);
As a member of the Z group (rubber having phosphorus and nitrogen in the main chain), rubber (FZ-P) having = N-chain and having a fluoroalkoxy group bonded to a phosphorus atom in the chain, = N-chain Rubbers (PZ-P) with allyloxy (phenoxy and substituted phenoxy) bonded to phosphorus atoms in the chain.

From the reason that a molded article having excellent durability can be obtained, the raw material rubber is preferably the M group (a rubber having a saturated main chain of a polymethylene type), the R group (a rubber having an unsaturated carbon bond in the main chain), It belongs to the Q group (rubber having silicon and oxygen in the main chain), and more preferably belongs to the M group and the R group.
Among the M groups, olefin rubbers such as ACM, EPM, EPDM, EVM, FEPM, EOM, and EBM are preferable, and EPM and EPDM are more preferable.
Among the R groups, butadiene rubber or isoprene rubber such as BR, IR, NR, NBR, SBR and HNBR are preferable, and HNBR and NBR are more preferable.

Examples of the thermoplastic plastic include thermoplastics described in JIS K 6899-1: 2015. Specifically, acrylonitrile-butadiene plastic (AB), acrylonitrile-butadiene-acrylate plastic (ABAK) acrylonitrile-butadiene-styrene plastic (ABS), acrylonitrile-chlorinated polyethylene-styrene (ACS), acrylonitrile- (ethylene- (Propylene-diene) -styrene plastic (AEPDS), acrylonitrile-methyl methacrylate plastic (AMMA), acrylonitrile-styrene-acrylate plastic (ASA), cellulose acetate (CA), cellulose acetate butyrate (CAB), cellulose acetate propionate (CAP), carboxymethylcellulose (CMC), cellulose nitrate (CN), cycloolefin copolymer (COC), Cellulose pionate (CP), cellulose triacetate (CTA), ethylene-acrylate plastic (EAA) ethylene-butyl acrylate plastic (EBAK), ethyl cellulose (EC), ethylene-ethyl acrylate plastic (EEAK), ethylene-methacryl Acid plastic (EMA), ethylene-propylene plastic (E / P), ethylene-tetrafluoroethylene plastic (ETFE), ethylene-vinyl acetate plastic (EVAC), ethylene-vinyl alcohol plastic (EVOH), perfluoro (ethylene-propylene) Plastic (FEP);

Poly [(3-hydroxybutyrate) -co- (3-hydroxyvalerate)] (HBV), liquid crystal polymer (LCP), methyl methacrylate-acrylonitrile-butadiene-styrene plastic (MABS), methyl methacrylate-butadiene- Styrene plastic (MBS), methylcellulose (MC), α-methylstyrene-acrylonitrile plastic (MSAN), polyamide (PA), polyacrylic acid (PAA), polyaryletherketone (PAEK), polyamideimide (PAI), polyacryl Acid ester (PAK), polyacrylonitrile (PAN), polyarylate (PAR), polyarylamide (PARA), polybutene (PB), polybutyl acrylate (PBAK), 1,2-polybutadiene (PB) ), Polybutylene naphthalate (PBN), polybutylene succinate (PBS), polybutylene succinate = adipate (PBSA), polybutylene terephthalate (PBT), polycarbonate (PC), polycyclohexylene dimethylene = cyclohexanedi Carboxylate (PCCE), polycycloolefin (PCO), polycaprolactone (PCL), polycyclohexylene dimethylene terephthalate (PCT), polychlorotrifluoroethylene (PCTFE);

Polyethylene (PE), polyethylene, chlorinated (PE-C), polyethylene, high density (PE-HD), polyethylene, low density (PE-LD), polyethylene, linear low density (PE-LLD), polyethylene, Medium density (PE-MD), polyethylene, ultra high molecular weight (PE-UHMW), polyethylene, very low density (PE-VLD), polyester carbonate (PEC), polyetheretherketone (PEEK), polyetherester (PEEST) , Polyether ketone (PEK), polyethylene naphthalate (PEN), polyethylene oxide (PEOX), polyethylene succinate (PES), polyether sulfone (PESU), polyethylene terephthalate (PET), polyether urethane (PEUR), perfluoro (Arki (Vinyl ether) -tetrafluoroethylene plastic (PFA), polyhydroxyalkanoate (PHA), poly (3-hydroxybutyrate) (PHB), polyisobutylene (PIB), polyketone (PK), polylactic acid (PLA), polymethacryl Imide (PMI), polymethyl methacrylate (PMMA), poly (N-methyl methacrylimide) (PMMI), poly (4-methylpent-1-ene) (PMP), poly (α-methylstyrene) (PMS), Polyoxymethylene, polyacetal, polyformaldehyde (POM), polypropylene (PP), polypropylene, impact (PP-HI), polypropylene, foaming (PP-E), polyphenylene ether (PPE), polypropylene oxide (PPOX), polyphenylene S Sulfide (PPS), polyphenylene sulfone (PPSU);

Polystyrene (PS), polystyrene, foaming (PS-E), polystyrene, impact resistance (PS-HI), polystyrene, sulfonation (PS-S), polystyrene, syndiotactic (PS-ST), polysulfone (PSU) ), Polytetrafluoroethylene (PTFE), polytrimethylene terephthalate (PTT), polyvinyl acetate (PVAC), polyvinyl alcohol (PVAL), polyvinyl butyral (PVB), polyvinyl chloride (PVC), polyvinyl chloride, chlorinated (PVC-C), polyvinyl chloride, non-plastic (PVC-U), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polyvinyl formal (PVFM), poly (N-vinyl) Carbazole) (PVK), poly (N-vinyl) Pyrrolidone) (PVP), styrene-acrylonitrile plastic (SAN), styrene-butadiene plastic (SB), styrene-maleic anhydride plastic (SMAH), styrene-α-methylstyrene plastic (SMS), vinyl chloride-ethylene plastic (VCE) ), Vinyl chloride-ethylene-methyl acrylate plastic (VCEMAK), vinyl chloride-ethylene-vinyl acetate plastic (VCEVAC), vinyl chloride-methyl acrylate plastic (VCCMAK), vinyl chloride-methyl methacrylate plastic (VCMMA), chloride Vinyl-octyl acrylate plastic (VCOAK), vinyl chloride-vinyl acetate plastic (VCVAC), vinyl chloride-vinylidene chloride plastic (VCDC) And the like.

Examples of the thermoplastic elastomer include those described in JIS K 6418: 2007. Specifically, an amide-based thermoplastic elastomer (TPA: a hard block is made of an amide bond, a soft block is made of an ether and / or an ester bond, and is a block copolymer composed of alternating hard segments and soft segments. Constituent); ester-based thermoplastic elastomer (TPC: the hard block of the main chain is made of ester bonds, and the soft block is made of ether and / or ester bonds. Olefinic thermoplastic elastomer (TPO: a blend of a polyolefin and a normal rubber, and the rubber phase of the blend has no or almost no crosslinking points); styrene-based thermoplastic Elastomer (TPS: polystyrene And a specific diene, a copolymer of at least 3 blocks, and two blocks (hard blocks) at both ends are polystyrene, and an inner block (one or more soft blocks) is a polydiene or Urethane-based thermoplastic elastomer (TPU: hard block is made of urethane bond, soft block is made of ether, ester, or carbonate bond, or a mixture thereof), and hard segment and hard segment are alternately formed. Thermoplastic rubber crosslinked product (TPV: a blend of thermoplastic resin and ordinary rubber, and this rubber is dynamically added during the blending or kneading process). Crosslinked by sulfuric acid); other thermoplastic elastomers (T Z: TPA, TPC, TPO, TPS, having composition or structure does not enter the classification of TPU and TPV) can be mentioned.

Among the thermoplastic resins, those having a low softening point are preferable, and for example, polyolefin-based thermoplastic resins such as PE, E / P, EVAC, and EEAK are preferable.
From the viewpoint of workability, the softening point of the thermoplastic resin is preferably higher than room temperature, more preferably 30 ° C. or higher, further preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher. Further, the softening point is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, and further preferably 110 ° C. or lower, from the viewpoint of ease of suppressing crosslinking.

Other than the specific examples of the rubber and the thermoplastic resin, for example, fluorine rubber; a polyethylene-based copolymer obtained by copolymerizing ethylene with a comonomer other than the above (meth) acrylate, tetracyclododecene, Other polyolefin resins such as polybutene-1 and polymethylpentene; other polyester resins such as hydroxybenzoic acid polyester; polymethacrylstyrene; and the like.
The resin crosslinkable by the radical may be a blended rubber or a blended resin of two or more kinds, and one kind or two or more kinds of rubbers and / or resins can be used.

The content of the resin capable of being crosslinked by radicals in the raw material composition is preferably 10 to 99% by mass relative to 100% by mass of the raw material composition. It is more preferably 20 to 90% by mass, and still more preferably 30 to 80% by mass.

<Other components (optional components)>
The raw material composition is added to a diene-based carboxylate and / or a compound that generates an anion represented by the formula (1) and a compound that generates a metal-containing cation, and a resin that can be cross-linked by radicals. , (1) a radical generator (often referred to as a crosslinking agent in the rubber field), (2) a crosslinking agent other than the radical generator, a crosslinking accelerator, a crosslinking accelerator, (3) a diene carboxylate (4) Fillers, (5) Processing aids such as softeners, plasticizers and solvents, (6) Anti-aging It may contain an agent, an antioxidant, a light stabilizer, an ultraviolet absorber, and (7) other additives. These may be used alone or in combination of two or more.

(1) Radical generator The raw material composition preferably further contains a radical generator. A raw material composition comprising: a diene carboxylate; and / or a compound capable of generating an anion and a metal-containing cation represented by the formula (1), and a radical-crosslinkable resin; Is also one of the preferred embodiments of the present invention.
The radical generator (often referred to as a crosslinking agent in the rubber field) is not particularly limited as long as it generates a radical in its structure by self-decomposition or the like in a crosslinking treatment step.
In the method for manufacturing a molded article of the present invention, when the raw material composition contains a radical generator, radicals generated from the radical generator are generated on the resin by abstracting hydrogen from the resin, and then a diene-based It is preferable to form a crosslinked structure by reacting with a carboxylate or another polyfunctional vinyl compound, and / or by coupling radicals generated in the resin.

Examples of the radical generator include a thermal radical generator that generates radicals by heating, a photoradical generator that generates radicals by irradiation with active energy rays, and the like.
As the above-mentioned thermal radical generator, those which generate radicals at a temperature higher than the kneading temperature are preferable. For example, the one-minute half-life temperature of the thermal radical generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. The one-minute half-life temperature of the thermal radical generator is preferably 270 ° C. or lower, more preferably 260 ° C. or lower, and further preferably 250 ° C. or lower.
Specific examples of the thermal radical generator include organic peroxides; sulfur; sulfur halides such as sulfur dichloride; and azo compounds.
One of these radical generators can be used alone or in combination of two or more.

Examples of the organic peroxide include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexylperoxy) -3,3. , 5-Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t- (Butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) ) Butane, 2,2-bis (4,4-di-t-butyl) -Oxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butylhydro Peroxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide , Di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl Peroxide, lauro Ruperoxide, stearoyl peroxide, succinic peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) per Oxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-s-butylperoxydicarbonate, di (3 -Methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutyl -Oxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy Isopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxy Simalate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxyisopropyl carbonate Butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (m-toluylper Oxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ′, 4,4'-tetra (t-butylperoxide (Xycarbonyl) benzophenone, 2,3-dimethyl-2,3-diphenylbutane and the like.

Examples of the azo compound include 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-) Carbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2 '-Azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N-phenylpropionamidine) Dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2 ' Azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2'-azobis [ 2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2 -(5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2 -(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, , 2'-Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3,4,5,6 -Tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'- Azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2 , 2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxye Tyl) propionamide], 2,2′-azobis (2-methylpropionamide), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis (2-methylpropane), Dimethyl-2,2-azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis [2- (hydroxymethyl) propionitrile] and the like. Can be

Radical generators that generate radicals upon irradiation with the active energy ray include alkylphenone-based compounds, benzophenone-based compounds, benzoin-based compounds, thioxanthone-based compounds, halomethylated triazine-based compounds, halomethylated oxadiazole-based compounds, biimidazole Compounds, oxime ester compounds, titanocene compounds, benzoate compounds, acridine compounds and the like.

Examples of the alkylphenone-based compound include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl Propionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl] -1-butanone, and the like.

Examples of the benzophenone-based compound include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 2-carboxybenzophenone, and the like.
Examples of the benzoin-based compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Examples of the thioxanthone-based compound include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone.
Examples of the halomethylated triazine-based compound include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl). -S-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbokinylnaphthyl) -4,6-bis (trichloromethyl) -s -Triazine and the like.

Examples of the halomethylated oxadiazole-based compound include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5- [β- (2′-benzofuryl). ) Vinyl] -1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.
Examples of the biimidazole-based compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis (2,2 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5′-tetraphenyl-1,2′-biimidazole and the like.
Examples of the oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, and 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.
Examples of the titanocene compound include titanocene compounds such as bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Compounds; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and 9-phenylacridine.

The radical generator is preferably an organic peroxide or sulfur, more preferably an organic peroxide, and even more preferably dicumyl peroxide or 1,1-di (t-hexyl peroxide). Oxy) cyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, n-butyl-4,4-di- (T-butylperoxy) valerate, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di (2 -T-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-hexyl peroxide, di-t-butyl peroxide, 2,5 Dimethyl-2,5-di (t-butylperoxy) hexine-3, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-methylbenzoyl) Peroxide, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, t-hexylperoxybenzoate, t-butylperoxybenzoate, di (2-methylbenzoyl) peroxide, particularly Preferably, it is dicumyl peroxide.

The content ratio of the radical generator in the raw material composition is preferably 0% by mass or more and 70% by mass or less based on 100% by mass of the radically crosslinkable resin.
When the raw material composition contains an organic peroxide, the content ratio of the organic peroxide is preferably 0% by mass or more, more preferably 100% by mass, based on 100% by mass of the radically crosslinkable resin. Is 0.1% by mass or more, more preferably 0.5% by mass or more. The content ratio of the organic peroxide in the raw material composition is preferably 15% by mass or less based on 100% of the radically crosslinkable resin. It is more preferably at most 12% by mass, further preferably at most 10% by mass.

(2) Cross-linking agents other than radical generators, cross-linking accelerators, and cross-linking accelerators The cross-linking agents other than the above-mentioned radical generators are not particularly limited, and for example, p-quinone dioxime, p, p'-dibenzoyl Quinoids such as quinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene; alkylphenol-formaldehyde resin, melamine-formaldehyde condensate, triazine-formaldehyde condensate, octylphenol-formaldehyde resin, alkylphenol-sulfide resin, hexa Resins such as methoxymethyl melamine resin; hexamethylene diamine carbamate, hexamethylene diamine, triethylene tetramine, tetraethylene pentamine, 4,4'-methylene bis (cyclohexylamine) carbamate Amines such as N, N'-dicinnamylidene-1,6-hexanediamine and ammonium benzoate; metal oxides such as zinc oxide, magnesium oxide, lead oxide and calcium oxide; 2,4,6-trimercapto- Triazine thiols such as s-triazine, 2-di-n-butylamino-4,6-dimercapto-s-triazine; polyols such as bisphenol A, bisphenol AF, hydroquinone, pentaerythritol, etc. Is mentioned.

As the cross-linking accelerator, those usually used can be used, and specifically, N-cyclohexyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazolesulfenamide, Sulfenamide vulcanization accelerators such as N-oxyethylene-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N, N'-diisopropyl-2-benzothiazolesulfenamide Guanidine-based vulcanization accelerators such as diphenylguanidine, diortitolylguanidine, ortho-tolylbiguanidine; thiourea-based vulcanization accelerator; thiazole-based vulcanization accelerator; thiuram-based vulcanization accelerator; dithiocarbamic acid-based vulcanization accelerator A xanthate-based vulcanization accelerator and the like.
As the cross-linking accelerator, those usually used can be used, and specific examples thereof include zinc oxide, stearic acid, and zinc stearate.

The total content of the cross-linking agent other than the radical generator in the raw material composition, the cross-linking accelerator and the cross-linking auxiliary agent is 0 to 15% by mass relative to 100% by mass of the radical-crosslinkable resin. Preferably, there is. More preferably, it is 1 to 10% by mass.

(3) Vinyl compounds other than diene carboxylate The vinyl compound other than diene carboxylate is not particularly limited, but unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid and the like. Metal salts such as zinc and magnesium; polyfunctional aromatic vinyl compounds such as divinylbenzene and divinylnaphthalene; isocyanurates such as triallyl isocyanurate and trimethallyl isocyanurate; cyanurates such as triallyl cyanurate; Maleimides such as N'-m-phenylenedimaleimide; polyallyl esters such as diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl fumarate, diallyl sebacate, triallyl phosphate; diethylene glycol bisallyl carbonate Polyallyl ethers such as ethylene glycol diallyl ether, triallyl ether obtained by allylating trimethylolpropane, and allyl ether obtained by partially allylating pentaerythritol; trimethylolpropane trimethacrylate and trimethylolpropane triacrylate; Examples include a polyfunctional (meth) acrylate compound.

The content ratio of the vinyl compound other than the diene carboxylate in the raw material composition is preferably 0 to 5% by mass based on 100% by mass of the radically crosslinkable resin. It is more preferably 0 to 3% by mass, and most preferably 0 to 1% by mass.

(4) Filler
As the filler, those commonly used can be used, and specifically, reinforcing fillers such as carbon black and silica; calcium carbonate, calcium silicate, magnesium oxide, aluminum oxide, barium sulfate, talc, mica And other non-reinforcing fillers.
In addition, plaster fiber, glass balun, silica balun, hydrotalcite, fly ash balun, shirasu balun, carbon balun, alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, glass fiber, cut fiber, rock fiber, micro Fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, recycled rubber, rubber powder, ebonite powder, shellac, wood powder, cellulose nanofiber, and the like can be given.
The content ratio of the filler in the raw material composition is preferably 0 to 500% by mass based on 100% by mass of the radically crosslinkable resin. More preferably, it is 5 to 300% by mass, and still more preferably 30 to 200% by mass.

(5) Processing aids such as softeners, plasticizers, and solvents In order to improve the mixing / dispersion of the components in the raw material composition and the processability, a softener, a plasticizer, a solvent, and a processing aid may be used. Good.
As the softener / plasticizer, those usually used can be used.Specifically, process oils, lubricating oils, paraffin, liquid paraffin, petroleum softeners such as petrolatum, castor oil, linseed oil, Rapeseed oil, fatty oil-based softeners such as coconut oil, tall oil, sub, beeswax, carnauba wax, waxes such as lanolin, linoleic acid, palmitic acid, stearic acid, lauric acid, phthalic ester compounds, polyester compounds, (Meth) acrylic oligomers and the like.
As the solvent, those usually used can be used, and specific examples thereof include toluene, xylene, ethylbenzene, cyclohexane, trimethylcyclohexane, and methyl isobutyl ketone.
The total content of the processing aids such as a softener, a plasticizer, and a solvent in the raw material composition is preferably 0 to 100% by mass relative to 100% by mass of the radically crosslinkable resin. . It is more preferably 5 to 50% by mass, and still more preferably 10 to 30% by mass.

(6) Antioxidants / antioxidants, light stabilizers, ultraviolet absorbers Antioxidants / antioxidants, light stabilizers, in order to more sufficiently prevent deterioration of molded articles obtained by the production method of the present invention. Agents and ultraviolet absorbers may be used.
Examples of antioxidants and antioxidants include various hindered phenol-based and phosphite-based ones.
Examples of the light stabilizer include hindered amine-based light stabilizers.
Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, and salicylic acid ester-based ones.
The total content of the antioxidant / antioxidant, the light stabilizer, and the ultraviolet absorber in the raw material composition is 0 to 10% by mass based on 100% by mass of the radically crosslinkable resin. Is preferred. It is more preferably 0 to 5% by mass, and still more preferably 0 to 0.53% by mass.
(7) Other additives As other additives, commonly used ones can be used, for example, a peptizer, a lubricant, a scorch inhibitor, a colorant, a release agent, a dispersant, a foaming agent. , A foaming aid, a flame retardant, a tackifier, an adhesion promoter, a wax, a coupling agent, a conductive agent, an acid acceptor, and a resin other than the above-mentioned radically crosslinkable resin.

<Kneading conditions>
In the kneading step of the present invention, all the components in the raw material composition may be mixed and kneaded at once, or may be mixed and kneaded in two or more stages. Further, a step of masticating the resin may be performed according to the type of the resin and the like.
In the kneading step, it is preferable (or may be used) for the kneading machine to use a mixing roll, a mixer, a kneader, an extruder, or the like, depending on the form of the raw material, the use of the obtained molded body, and the like.
In the kneading step, the kneading is preferably performed at a temperature at which a large amount of radicals are not generated, that is, at a temperature at which a crosslinking reaction does not occur in a radical-crosslinkable resin. When the raw material composition contains a radical generator, it is preferable to knead the mixture at a temperature at which the radical generator does not react. The kneading temperature may be set according to the type of resin (melting point or Mooney viscosity), but is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 160 ° C. or lower. The kneading temperature is usually preferably 30 ° C. or higher, more preferably 50 ° C. or higher.
It is preferable to control the kneading temperature by controlling, for example, the number of rotations of a roll of a kneading apparatus, the number of rotations of kneading blades, cooling water, and the like.

≪Molding process≫
The method for producing a molded article of the present invention includes a step of molding the composition before the crosslinking treatment and / or the crosslinked article after the crosslinking treatment.
Here, molding refers to adjusting the shape, and in the molding step, the kneaded composition obtained in the kneading step is, for example, a sheet, a film, a pellet, a layer, a rod, a sphere, and a particle. , Powder, member for various applications, etc.

The method of molding the composition and / or the crosslinked body in the molding step is not particularly limited, but is processed into a desired shape by, for example, extrusion, injection, pressure, rolling, release treatment, cutting, cutting, or polishing. May be.
For the molding, for example, a commonly used molding machine such as an extrusion molding machine, an injection molding machine, a pressure molding machine, or a mold may be used.

≪Cross-linking process≫
The method for producing a molded article of the present invention includes a step of generating a radical in the composition after the kneading step and performing a crosslinking treatment. The composition subjected to the crosslinking treatment may be a composition before the molding step or a composition after the molding step, as long as it is a composition after the kneading step.
In the cross-linking treatment step, the method for generating radicals is not particularly limited, and examples thereof include heating and irradiation with active energy rays. Further, the generation of the radical may be performed only by irradiation with an active energy ray without using the radical generator described above. When a radical generator is used in the kneading step, it may be appropriately selected according to the radical generator used, and the above methods may be used in combination.

As the active energy ray, those commonly used can be used, and examples thereof include gamma rays, X-rays, ultraviolet rays, visible rays, electromagnetic waves such as infrared rays, and electron beams, neutron rays, and particle beams such as proton rays. .

In the crosslinking treatment step, a method of generating radicals is preferably a method of heating.
The heating temperature is not particularly limited as long as radicals are generated, but is preferably 100 ° C. or higher. The temperature is more preferably 120 ° C. or higher, and still more preferably 140 ° C. or higher. Further, the temperature is preferably 300 ° C. or lower, more preferably 260 ° C. or lower.
The crosslinking treatment by heating may be performed in one stage, or may be performed in two or more stages by changing the heating temperature.
The heating time is not particularly limited, but is preferably, for example, 10 seconds to 100 hours. More preferably, it is 1 minute to 24 hours.
In addition, a 90% vulcanization time may be determined in accordance with JIS K 6300-2: 2001, and the heating time may be set based on this.

The cross-linking treatment step may be performed simultaneously with the molding step, as described above. For example, the molding and the cross-linking treatment are performed at the same time by heating while performing molding by a molding machine in the molding step.

2, a diene-based carboxylate, and / or a compound that generates an anion and a compound that generates a metal-containing cation represented by Formula (1), and a resin that generates a crosslinkable active site in the structure by a radical. The composition containing the present invention also includes a salt (a diene carboxylate) containing the anion represented by the above formula (1) and a metal-containing cation, and / or a compound that generates the anion and the metal-containing cation. The composition also includes a compound to be generated and a resin that generates a crosslinkable active site in the structure by a radical.
The composition may include a diene carboxylate, a compound that generates the anion and a compound that generates the metal-containing cation, and other components other than the resin, and may further include a radical generator. Is preferred.
Each component in the composition is as described in the raw material composition in the kneading step of the method for producing a molded article. The preferred ratio of each component in the composition is the same as the preferred ratio of each component in the raw material composition.

3. Molded product (cross-linked product)
The present invention also relates to a method wherein a crosslinkable active site is generated in a structure by a structural unit represented by the formula (2) and / or the formula (3), and the radical is represented by the formula (2) or (3). And a structural unit derived from a resin having no structural unit represented by the formula (1).
Here, the crosslinked body refers to a rubber or a resin obtained by three-dimensionally crosslinking a resin.

The structural unit represented by the formula (2) and / or the formula (3) is a structural unit derived from a salt (diene carboxylate) containing the anion represented by the formula (1) and a metal-containing cation. And a structural unit having the same structure as the structure formed by polymerization of the diene carboxylate.
However, the structural unit derived from the diene carboxylate is not limited to the structural unit actually formed by polymerization of the diene carboxylate. If the diene carboxylate has the same structure as the structure formed by polymerization, the structural unit formed by another method is also included in the structural unit derived from the diene carboxylate.
The diene carboxylate is as described in the method for producing a molded article.
For example, when the diene-based carboxylate is 2-((meth) allyloxymethyl) acrylate, the structural unit derived from the salt is represented by the following formula (5) and / or (6);

(In the formula, M is a metal-containing cation.)

As a resin that generates a crosslinkable active site in the structure by a radical and does not have the structural units represented by Formulas (2) and (3) (the structural units derived from the diene carboxylate), The rubber and the thermoplastic resin described in the method for producing a molded body are exemplified. Specific examples and preferred examples are as described above.

In the crosslinked product, the proportion of the structural unit represented by the formula (2) and / or the formula (3) is such that a radical generates a crosslinkable active site in the structure, and the formula (2) and ( It is preferably 0.5% by mass or more based on 100% by mass of a structural unit derived from a resin not having the structural unit represented by 3) (the structural unit derived from the diene carboxylate). Moreover, it is preferable that it is 70 mass% or less. Thereby, the appearance uniformity, mechanical strength, and adhesion of the crosslinked body are further improved. It is more preferably at least 2% by mass. Further, the content is more preferably 60% by mass or less, further preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less. It is.

The crosslinked product is one in which a crosslinkable active site is generated in the structure by the structural unit and the radical represented by the formula (2) and / or the formula (3), and is represented by the formulas (2) and (3). It may have other structural units other than the structural unit derived from the resin having no structural unit.
Other structural units are not particularly limited, for example, a structural unit derived from a radical generator in the method for producing a molded article, a structural unit derived from a crosslinking agent other than the radical generator, other than a diene carboxylate. And a structural unit derived from a vinyl compound.

In the crosslinked product, the ratio of the other structural unit is such that a radical generates a crosslinkable active site in the structure, and the resin has no structural unit represented by the formula (2) or (3). It is preferably from 0 to 1000% by mass relative to 100% by mass of the derived structural unit. It is more preferably 0 to 500% by mass, further preferably 0 to 100% by mass, further preferably 0 to 50% by mass, particularly preferably 0 to 10% by mass, and most preferably 0% by mass. It is.

The method for producing the crosslinked body is not particularly limited, but is preferably produced by the above-described method for producing a molded body. That is, the crosslinked product is preferably a molded product obtained by the production method of the present invention.

The crosslinked product of the present invention and the molded product obtained by the production method of the present invention can be used for various applications, for example, electric insulating materials, sealing materials, sealing materials, vibration-proof rubbers, structural members such as automobiles It is suitably used for industrial applications such as

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples. Unless otherwise specified, “parts” means “parts by mass” and “%” means “% by mass”.

<Synthesis example 1>
2- (allyloxymethyl) acrylate ion (AOMA ⁻ ) and zinc ion (Zn ²⁺ )
(Zinc 2- (allyloxymethyl) acrylate: AOMA-Zn)
[Synthesis of aqueous solution of sodium 2- (allyloxymethyl) acrylate]
In total, 84.0 parts of methyl 2- (allyloxymethyl) acrylate (AOMA-M) and 21.3 parts of NaOH were divided into 12 parts so that the methanol concentration in the reaction solution did not exceed 3%. Hydrolysis was performed while charging and removing methanol.
A reactor equipped with a stirrer, a temperature sensor, a gas inlet tube, a U-shaped tube, a cooling tube, and a distillation receiver is charged with 100.0 parts of ion-exchanged water, and while stirring, an oxygen / nitrogen mixed gas (oxygen (Concentration 7%, volume / volume), and the temperature was raised to 40 ° C. by an oil bath.
(Hydrolysis of the first division)
7.0 parts of AOMA-M and 3.7 parts of a 48% NaOH aqueous solution (0.99 equivalents based on AOMA-M) are sequentially charged, and after stirring for 5 minutes, the pressure in the reactor is adjusted to 6.7 kPa. The pressure was gradually reduced, and water containing methanol was distilled out while adjusting the heating with an oil bath so that the internal temperature became 40 to 45 ° C. When the liquid volume in the distilling receiver reached approximately 27 parts, the pressure was released, the oil bath was lowered, heating was interrupted, and the distillate volume was weighed.
(Hydrolysis of the second division)
3.7 parts of a 48% NaOH aqueous solution was diluted with ion-exchanged water so as to obtain an NaOH aqueous solution having the same weight as the distillate amount of the first division. 7.0 parts of AOMA-M and an aqueous NaOH solution are sequentially charged, and after stirring for 5 minutes, the pressure in the reactor is gradually reduced until the pressure in the reactor reaches 6.7 kPa, and an oil bath is set so that the internal temperature becomes 40 to 45 ° C. The water containing methanol was distilled off while adjusting the heating by. The pressure was released when the amount of distillate reached approximately 27 parts, the oil bath was lowered, heating was interrupted, and the amount of distillate was weighed.
(Hydrolysis of 3rd to 12th divisions)
The operation was performed in the same manner as in the hydrolysis of the second division.

[Synthesis of 2- (allyloxymethyl) acrylic acid]
After the operation of the 12th division was completed, the reaction solution was cooled to room temperature, and 27.0 parts of sulfuric acid was added dropwise over 1 hour while cooling in a water bath. After the completion of the dropping, the content liquid was transferred to a separating funnel and allowed to stand for 1 hour. The lower aqueous layer was discarded, and the upper organic layer (2- (allyloxymethyl) acrylic acid containing water) was separated.
[Synthesis of zinc 2- (allyloxymethyl) acrylate]
A stirrer, a separated organic layer, 220.0 parts of ethyl acetate, and 0.05 part of 6-t-butyl-2,4-xylenol were placed in a reaction vessel equipped with a thermometer, and stirred with a magnetic stirrer. While cooling in a water bath, 21.7 parts of zinc oxide powder was added little by little so that the internal temperature did not exceed 40 ° C. After adding all the zinc oxide powder, the mixture was stirred for 2 hours. The reaction solution was filtered with a filter having a pore size of 0.45 μm, and the filtrate was placed in a container equipped with a stirrer, a temperature sensor, a gas inlet tube, a U-shaped tube, a cooling tube, and a distillation receiver. The pressure was reduced while heating so as not to exceed, and ethyl acetate and water were distilled off. The viscous contents were transferred to a plastic container while still warm, yielding 80.0 parts of zinc 2- (allyloxymethyl) acrylate.

<Examples 1-3, Comparative Examples 1-3>
Using EPDM (classified as M group (raw rubber having a polymethylene-type saturated main chain) in JIS K 6397: 2005) as a resin, preparation, kneading, molding, and crosslinking treatment of a crosslinkable resin composition as described below Was performed to obtain a molded body.
(Preparation and kneading of crosslinkable resin composition)
Each raw material was prepared at the compounding ratio shown in Table 1 so that the total mass of the raw materials would be 600 parts, and an open roll machine (manufactured by Takamuro Ironworks Co., Ltd., roll size: diameter 8 inches × width 18 inches) The kneading was performed at a roll rotation speed of 18 rpm and a front and rear roll rotation ratio of 1: 1.25.

(Production of vulcanized sheet (molded product) (molding and crosslinking))
Die vulcanization test A method (test temperature: 160) in accordance with JIS K 6300-2: 2001 "Unvulcanized rubber-physical properties-Part 2: Determination of vulcanization characteristics using vibration type vulcanization tester" 90 ° C., amplitude angle: ± 1 °, frequency: 1.67 Hz), the 90% vulcanization time of the crosslinkable resin composition was determined, and this was taken as the vulcanization time. Table 1 shows the results.
Press molding was performed at 160 ° C. for the set vulcanization time to produce a 15 cm square, 2 mm thick vulcanized sheet.
The appearance uniformity, mechanical strength, and adhesion of the obtained molded body were evaluated by the following methods.

(Evaluation of appearance uniformity)
The surface of the vulcanized sheet was visually observed, and the uniformity of appearance was evaluated according to the following criteria. Table 1 shows the results.
：: uniform and glossy over the entire surface △: whitening is observed on the surface, but the gloss partially remains ×: whitening is entirely observed and there is no gloss

(Evaluation of mechanical strength)
・ Durometer hardness
According to JIS K 6253-3: 2012 "Vulcanized rubber and thermoplastic rubber-Determination of hardness-Part 3: Durometer hardness", a dumbbell-shaped No. 3 obtained by punching a vulcanized sheet. Of three dumbbell test pieces were laminated, and the durometer hardness was measured using a type A durometer. Table 1 shows the results.
・ Tensile strength, elongation at break In accordance with JIS K 6251: 2010 “Vulcanized rubber and thermoplastic rubber-Determination of tensile properties”, a vulcanized sheet is punched and a dumbbell-shaped No. 3 dumbbell specimen is prepared. It was prepared and the tensile strength and elongation at break were measured using a tensile tester. Table 1 shows the results.
・ Tear strength JIS K 6252-1: 2015 "Vulcanized rubber and thermoplastic rubber-Determination of tear strength-Part 1: Method using trouser, angle and crescent test specimens" The sulfuric acid sheet was stamped to form an angle-shaped test piece with no cut, and the tear strength was measured using a tensile tester. Table 1 shows the results.

(Evaluation of adhesion)
In accordance with JIS K 6256-2: 2013 "Vulcanized rubber and thermoplastic rubber-Determination of adhesiveness-Part 2: 90 ° peel strength with rigid plate", the crosslinkable resin composition is applied to a metal plate. A test piece was prepared by sulfuric acid bonding (direct bonding), and the peel strength was measured with a tensile tester. The vulcanization adhesion was performed at the same temperature and time as in the production of the vulcanized sheet. Three types of metal plates were evaluated: an aluminum plate (A1050P), a stainless steel plate (SUS304), and a rolled steel plate (SS400). Table 1 shows the results. In addition, the sample which could not produce a test piece because it did not adhere to the metal plate at all by vulcanization adhesion was regarded as "test impossible".

<Examples 4 and 5, Comparative Examples 4 and 7>
Using NBR (classified as R group (raw rubber having an unsaturated carbon bond in the main chain) in JIS K 6397: 2005) as a resin, preparation, kneading, molding, and crosslinking treatment of a crosslinkable resin composition as described below Was performed to obtain a molded body.
(Preparation and kneading of crosslinkable resin composition)
Each raw material was prepared at a mixing ratio shown in Table 2 so that the total mass of the raw materials was 600 parts. Using a kneader (manufactured by Naniwa Kikai Co., Ltd.), the raw materials other than the crosslinking agent, co-crosslinking agent and vulcanization accelerator were rotated at a front blade rotation speed of 50 rpm, a front and rear blade rotation ratio of 1.6: 1.3, a can body temperature of 110 ° C., Kneading was performed under the conditions of a kneading time of 20 minutes. Next, using an open roll machine (manufactured by Ikeda Machine Industry Co., Ltd., roll size: 6 inches in diameter × 15 inches in width), the resin composition kneaded with a kneader, a crosslinking agent, and a co-crosslinking agent were rolled forward at a rotational speed of 19 rpm and rolled back and forth. Kneading was performed at a rotation ratio of 1: 1.25.

(Preparation of vulcanized sheet (molded body) (molding and crosslinking)
Vulcanized sheets were produced in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3.
(Evaluation of the physical properties)
About the obtained molded object, external appearance uniformity, mechanical strength, and adhesiveness were evaluated like Example 1-3 and Comparative Examples 1-3. Table 2 shows the results.

The details of each component described in Tables 1 and 2 below are as follows.
resin:
Ethylene propylene diene rubber (EPDM), manufactured by JSR, EP21 (middle ENB)
Middle and High Nitrile NBR (Middle and High NBR), manufactured by JSR, N230S (Middle and High Nitrile)
Low Nitrile NBR (Low NBR), manufactured by JSR, N250S (Low Nitrile)
filler:
Carbon black (CB), manufactured by Asahi Carbon Co., Ltd., HAF carbon black silica (SiO ₂ ), softener / plasticizer manufactured by Tosoh Silica Co .:
Naphthenic oil (NOL), di-2-ethylhexyl phthalate (DOP) manufactured by JXTG Energy, cross-linking agent manufactured by Nippon Rika Co., Ltd .:
Dicumyl peroxide (DCPO), manufactured by NOF Corporation, Parkmill D-40
Crosslinking promotion / promoting aid:
Zinc oxide II (ZnO), Stearic acid (STA) manufactured by Hakusui Tech, Co-crosslinking agent manufactured by NOF Corporation:
Diene carboxylate (AOMA-Zn) obtained in Synthesis Example 1
Zinc acrylate (ZnDA), manufactured by Nisshin Techno Fine Chemical Company Zinc methacrylate (ZnDMA), manufactured by Nisshin Techno Fine Chemical Company

As can be seen from the comparison between Comparative Examples 1 and 2 and Comparative Example 3, by adding ZnDA and ZnDMA, the hardness, tensile strength, and tear strength are improved, and adhesion to a metal plate is exhibited. However, although the adhesion is improved by adding ZnDA, the elongation at break is remarkably reduced, resulting in hard and brittle mechanical strength characteristics and extremely poor appearance uniformity. In addition, when ZnDMA is added, a well-balanced mechanical strength is exhibited, but the adhesion is not sufficient. On the other hand, by adding AOMA-Zn, both hardness and elongation at break are compatible, the tear strength is strong, the mechanical strength is excellent, and the adhesion and the uniformity of appearance are also good. In particular, in Example 3, in which the amount of AOMA-Zn added was increased, while exhibiting extremely high adhesion, it exhibited a high elongation equivalent to that in which no co-crosslinking agent was added (Comparative Example 3). It is considered that such a result is due to the fact that AOMA-Zn is easily compatible with the raw material resin, has high polymerization activity, and generates a ring structure in the main chain by polymerization.

From the comparison between Comparative Examples 4 and 5 and Comparative Example 6, although the hardness and tensile strength are improved by adding ZnDA and ZnDMA, the elongation is significantly reduced, and particularly, the elongation is significantly reduced in ZnDA. I understand. On the other hand, AOMA-Zn (Example 4) shows high elongation while showing high hardness and tensile strength, and has well-balanced mechanical strength. Further, from the comparison between Example 5 and Comparative Example 7, even when a low-polarity raw material resin (low NBR) having a low nitrile content is used, good appearance uniformity is exhibited by adding AOMA-Zn. I understand. Such a result is considered to suggest that AOMA-Zn is well compatible with low-polarity raw material resins.

Claims (7)

Formula (1) below;

(In the formula, R represents a hydrogen atom or a methyl group. X ¹ , Y ¹ and Z ¹ are the same or different and each represents a methylene group which may have a substituent or an oxygen atom. However, at least one of X ¹ , Y ^1, and Z ¹ is an oxygen atom, and a bond of an oxygen atom—a carbon atom—an oxygen atom represented by a dotted line and a solid line corresponds to two bonds included in the bond. A carbon atom-oxygen atom bond is equivalent, and the entire bond of the oxygen atom-carbon atom-oxygen atom is a monovalent anion.) And a metal-containing cation. And / or a step of kneading a composition containing a compound that generates the anion and a compound that generates the metal-containing cation, and a resin that generates a crosslinkable active site in the structure by a radical.
A step of subjecting the composition after the kneading step to a crosslinking treatment by generating radicals;
Molding the composition before the crosslinking treatment and / or the crosslinked body after the crosslinking treatment. The method according to claim 1, wherein the composition further includes a radical generator. The method according to claim 1, wherein the resin includes a rubber and / or a thermoplastic resin. The method according to claim 1, wherein the metal-containing cation is a metal ion. Formula (1) below;

(In the formula, R represents a hydrogen atom or a methyl group. X ¹ , Y ¹ and Z ¹ are the same or different and each represents a methylene group which may have a substituent or an oxygen atom. However, at least one of X ¹ , Y ^1, and Z ¹ is an oxygen atom, and a bond of an oxygen atom—a carbon atom—an oxygen atom represented by a dotted line and a solid line corresponds to two bonds included in the bond. A carbon atom-oxygen atom bond is equivalent, and the entire bond of the oxygen atom-carbon atom-oxygen atom is a monovalent anion.) And a metal-containing cation. And / or a compound that generates the anion and the compound that generates the metal-containing cation, and a resin that generates a crosslinkable active site in the structure by a radical. The composition according to claim 5, wherein the composition further contains a radical generator. Formula (2) and / or Formula (3) below;

(In the formula, R represents a hydrogen atom or a methyl group. X ¹ , Y ¹ and Z ¹ are the same or different and each represents a methylene group which may have a substituent or an oxygen atom. However, at least one of X ¹ , Y ^1, and Z ¹ is an oxygen atom, and M represents a metal-containing cation.) And an activity capable of being cross-linked into the structure by a radical. And a structural unit derived from a resin having no structural unit represented by formulas (2) and (3).

Images