JP4955964B2 - Method for producing thermoplastic partially crosslinked resin molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a thermoplastic partial cross-linkage resin molding body that is excellent in fire retardancy, heat resistance, and mechanical characteristics and is corresponding to the environmental problem of these days in which when disposing by the filling in land, the combustion or the like, there is not the elution of the heavy metal compound, a lot of smoke, and the generation of harmful gas. <P>SOLUTION: The manufacturing process of a thermoplastic partial cross-linkage resin molding body comprises: the first process which carries out the melting and kneading of a mixture containing (e) 30-300 mass pts. of a metal hydrate and (f) 0-2.0 pts.mass of a (meth)acrylate base and/or allyl base cross-linkage auxiliary agent based on 100 mass pts. of a thermoplastic resin composition to obtain a resin composition; the second process which makes (g) 0.02-1.0 pts.mass of an organic peroxide based on 100 pts.mass of thermoplastic resin composition and the third process in which the resin composition obtained from the first and second processes is molded while heating at the temperature not lower than the organic peroxide decomposition temperature. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a thermoplastic partially cross-linked resin molded body, and more specifically, elution of heavy metal compounds, generation of a large amount of smoke and harmful gas, recycle after use, and special cross-linking equipment. The present invention relates to a method for producing a thermoplastic partially cross-linked resin molded product that does not require the above.

  In recent years, non-halogen flame retardant materials have been studied in consideration of the environment. Non-halogen flame retardant materials express flame retardancy by blending a flame retardant containing no halogen into the resin. For example, aluminum hydroxide, magnesium hydroxide, etc. as a flame retardant for resins such as ethylene copolymers A material containing a large amount of the above metal hydrate is used as a wiring material.

  Standards such as flame retardancy, heat resistance, and mechanical properties (for example, tensile properties and wear resistance) required for wiring materials of electric / electronic devices are defined by UL, JIS, and the like. In particular, for flame retardancy, the test method varies depending on the required level (its application) and the like. Therefore, in practice, it is only necessary to have flame retardancy according to at least the required level. For example, the vertical flame test (VW-1) defined in UL1581 (Reference Standard for Electrical Wires, Cables and Flexible Cords) (VW-1), JIS C 300 Examples include flame retardancy that passes the horizontal test and inclination test specified in (Rubber / Plastic Insulated Wire Test Method).

  Of these, when a non-halogen flame retardant material is imparted with a high degree of flame retardancy that passes VW-1 or a gradient test, metal hydration, which is a flame retardant, is added to 100 parts by weight of the resin component. It is necessary to blend 150 to 200 parts by weight of the product, and as a result, there is a problem that mechanical properties such as tensile properties and wear resistance of the coating material are remarkably deteriorated.

Moreover, about the molded object used for an electrical / electronic device, the heat resistance of 80 to 105 degreeC may be requested | required in the state of continuous use.
In such a case, for the purpose of imparting high heat resistance to the wiring material, a method of crosslinking the coating material by an electron beam crosslinking method or a chemical crosslinking method is employed.

  However, it has been pointed out that the cross-linked wiring material has improved heat resistance of the coating material, but cannot be remelted, so that it is difficult to reuse and recyclability is poor. For example, when recovering metals used in conductors, it is often necessary to burn the coating, etc., and avoid the environmental problems associated with conventional coatings containing halogen or phosphorus. I can't. Furthermore, special equipment such as electron beam cross-linking equipment and chemical cross-linking equipment must be prepared, resulting in high equipment costs and high cost of the molded body, which causes a decrease in versatility.

  On the other hand, as a method for realizing heat resistance of about 80 ° C. to 105 ° C. with a molded body that is not subjected to crosslinking as described above, there is a method using a resin having a high melting point such as a polypropylene resin. However, although such a resin has good heat resistance, it is poor in flexibility, and when the molded body covering it is bent, the phenomenon of whitening of the surface is observed.

In view of this, studies have been made to form a coating layer of a wiring material using a partially crosslinked compound obtained by crosslinking a part of a resin so as to have a property intermediate between crosslinked and non-crosslinked. However, since a part of the material is already cross-linked at the time of molding, the load at the time of molding is high. For example, a material having a large amount of metal hydrate is poor in mass production, and special equipment has to be prepared.
JP 2000-315424 A JP 2001-316537 A JP 2002-114878 A

  The present invention solves the above-mentioned problems, has a low load during molding, is excellent in mass productivity, and can be used to produce a molded product without using special equipment. The purpose is to provide.

In order to solve the above problems, the present invention provides:
(1) The thermoplastic resin component contains 60-100% by mass of resin and (d) 0-40% by mass of plasticizer and / or oil, and the resin is (a) polyethylene, polypropylene, ethylene / α-olefin copolymer Polyolefins selected from polymers, ethylene / vinyl acetate copolymers, ethylene / (meth) acrylic acid ester copolymers, ethylene / (meth) acrylic acid copolymers and binary or ternary copolymer acrylic rubbers Resin, (b) polyethylene, polypropylene, ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer and ethylene / modified with an unsaturated carboxylic acid or derivative thereof A polymer selected from (meth) acrylic acid copolymers, and (c) a group of styrenic elastomers. It is selected, and for at least the ethylene-vinyl acetate copolymer (a) contains more than 70 wt%, the thermoplastic resin to 100 parts by weight of the component in the thermoplastic resin component, (e) metal hydrosulfide A first step of melt-kneading a mixture containing 30 to 300 parts by weight of a Japanese product, 0 to 2.0 parts by weight of an (meth) acrylate-based and / or allylic crosslinking aid to obtain a resin composition; A second step of dispersing 0.02 to 1.0 parts by mass of organic peroxide (g) in the resin at a temperature at which it does not decompose with respect to 100 parts by mass of the thermoplastic resin component, a first step and a second step A method for producing a thermoplastic partially crosslinked resin molded article, characterized by comprising a third step in which the resin composition obtained in the step is molded and crosslinked while being heated at an organic peroxide decomposition temperature or higher,
(2) The thermoplastic resin component contains 60-100% by mass of resin and (d) 0-40% by mass of plasticizer and / or oil, and the resin is (a) polyethylene, polypropylene, ethylene / α-olefin copolymer Polyolefins selected from polymers, ethylene / vinyl acetate copolymers, ethylene / (meth) acrylic acid ester copolymers, ethylene / (meth) acrylic acid copolymers and binary or ternary copolymer acrylic rubbers Resin, (b) polyethylene, polypropylene, ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer and ethylene / modified with an unsaturated carboxylic acid or derivative thereof A polymer selected from (meth) acrylic acid copolymers, and (c) a group of styrenic elastomers. Composed of at least one resin selected, and thermoplastic at least the ethylene-vinyl acetate copolymer (a) contains more than 70 wt% in the resin component, the thermoplastic resin 100 parts by weight of component On the other hand, a composition containing (e) 30 to 300 parts by mass of a metal hydrate, (f) (meth) acrylate-based and / or allylic crosslinking aid 0 to 2.0 parts by mass is melt-kneaded. After obtaining the resin composition, 0.02 to 1.0 part by mass of (g) organic peroxide is dispersed with respect to 100 parts by mass of the thermoplastic resin component, and at the same time heating at an organic peroxide decomposition temperature or higher. A method for producing a thermoplastic partially crosslinked resin molded product, characterized by molding and crosslinking,
(3) The method for producing a thermoplastic partially crosslinked resin molded article according to (1) or (2), wherein 50% by mass or more of the metal hydrate is treated with a silane coupling agent,
(4) The method for producing a thermoplastic partially crosslinked resin molded article according to (3), wherein the silane coupling agent has a reactive group at a terminal.
(5) The method for producing a thermoplastic partially crosslinked resin molded article according to any one of (1) to (4), wherein the metal hydrate is magnesium hydroxide,
(6) The method for producing a thermoplastic partially crosslinked resin molded article according to any one of (1) to (5), wherein the thermoplastic partially crosslinked resin molded article is molded by extrusion molding,
Is to provide.

The production method of the present invention is a production method capable of obtaining a thermoplastic partially crosslinked resin molded article by performing partial crosslinking at the same time as molding, without requiring special equipment for extrusion molding. is there.
Furthermore, the production method of the present invention is a method for producing an excellent thermoplastic partially crosslinked resin molded article having a low load during molding and high mass productivity.

In the present invention, since the fine cross-linking is performed at the time of molding the molded body, the load at the time of molding can be significantly reduced as compared with the case of molding a compound that has been subjected to micro-crosslinking in advance. Therefore, it is possible to mold without using a crosslinking aid. Further, when a crosslinking aid is added, since the crosslinking aid does not react at the start of extrusion, it also acts as a lubricant and can greatly reduce the extrusion load.
Hereinafter, each component used in the present invention will be described in detail.

(A) Polyolefin resin In the present invention, a polyolefin resin can be used.
Polyolefin resins used in the present invention include polyethylene, polypropylene, ethylene · alpha-olefin copolymer, ethylene-vinyl acetate copolymers, ethylene (meth) acrylic acid ester copolymer, ethylene (meth) acrylic acid copolymer, It is selected from binary copolymer acrylic rubber and ternary copolymer acrylic rubber.

Specifically, for example, NUC polyethylene (trade name, manufactured by Nihon Unicar Co., Ltd.), Sun Allomer (trade name, manufactured by Sun Allomer Co., Ltd.), Everflex (trade name, manufactured by Mitsui Dupont Polychemical Co., Ltd.), Baymac ( Trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.).
As the polyolefin resin of the present invention, only one type may be used or two or more types may be mixed and used.

(B) Polyolefin resin modified with an unsaturated carboxylic acid or derivative thereof In the present invention, a polyolefin modified with an unsaturated carboxylic acid or derivative thereof can be used.
Polyolefins modified with unsaturated carboxylic acids or derivatives thereof include polyethylene, polypropylene, ethylene / α-olefin copolymers, ethylene vinyl acetate copolymers, ethylene (meth) acrylate copolymers, ethylene (meth) A resin obtained by modifying an acrylic acid copolymer or the like with an unsaturated carboxylic acid or a derivative thereof. Examples of the unsaturated carboxylic acid used for the modification include maleic acid, itaconic acid, fumaric acid, and acrylic acid. The unsaturated carboxylic acid derivatives include maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester, fumaric anhydride, There are acrylic acid esters. In the present invention, polyethylene, polypropylene, ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer and ethylene / modified with an unsaturated carboxylic acid or derivative thereof are used. It is selected from (meth) acrylic acid copolymers.
The modification of the polyolefin can be performed, for example, by melting and kneading the polyolefin and the unsaturated carboxylic acid in the presence of the organic peroxide. The modification amount of the carboxylic acid is usually about 0.5 to 7% by weight.

In the present invention, as the polyolefin modified with an unsaturated carboxylic acid or a derivative thereof, only one kind may be used, or two or more kinds may be mixed and used.
Specific examples include Adtex (trade name, manufactured by Nippon Polyolefin Co., Ltd.) and P-1002 (trade name, manufactured by Crompton).

  Polyolefins modified with unsaturated carboxylic acids are effective as adhesives for resins and fillers, as compatibilizers for ethylene copolymers and styrene elastomers, styrene grafters, and ethylene propylene rubber. This has the effect of suppressing the decrease in insulation resistance and the effect of increasing the strength of the compound.

(C) Styrenic elastomer In the present invention, a styrenic elastomer can be used.
Styrenic elastomers are block copolymers, random copolymers, or those obtained by hydrogenation of at least one polymer block S of styrene and polymer block B mainly composed of a conjugated diene compound. Or a mixture thereof. Specific examples include Dynalon (trade name, manufactured by JSR Corporation).
As these conjugated diene compounds, for example, one or more types are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and These combinations are preferred.

  When adding a styrene-type elastomer in this invention, Preferably it is 30 mass% or less in 100 weight% of resin components, More preferably, it is 5-30 mass%. When the amount of the styrene elastomer is too large, not only the extrusion processability of the coating material is remarkably deteriorated, but also the elongation property and the strength are remarkably deteriorated.

In the present invention, the resin of the resin molded body is composed of at least one resin of the group consisting of (a), (b) and (c). In the present invention, any one of the components (a), (b) and (c) may be used, or two or more may be used in combination.
However, the resin of the resin molded body of the present invention contains at least 70% by mass or more of the ethylene / vinyl acetate copolymer (a) in the thermoplastic resin component.

(D) Plasticizers and / or oils In the present invention, non-aromatic mineral oils such as plasticizers and / or oils, or liquid or low molecular weight synthetic softeners can be used. Specific examples include Diana Process PW90 (trade name, manufactured by Idemitsu Kosan Co., Ltd.). By using the plasticizer and / or oil in common with acrylic rubber or styrene-based elastomer, bleed can be suppressed and flexibility can be exhibited.

  The compounding quantity of a component (d) is 0-40 mass%, Preferably, it is 0-15 mass%. If the blending amount is too large, the plasticizer and / or oil may bleed out, giving the molded article stickiness, and the mechanical properties may be lowered.

(E) Metal Hydrate The metal hydrate used in the present invention is not particularly limited. For example, aluminum hydroxide, magnesium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, A compound having a hydroxyl group or crystal water such as hydrotalcite can be used alone or in combination of two or more. Among these, use of magnesium hydroxide is preferable.

  In the metal hydrate of this invention, you may surface-treat. In particular, it is preferable to use a metal hydrate that has been surface-treated with a silane coupling agent. Examples of the metal hydrate subjected to surface treatment with a silane coupling agent include “Kisuma 5L” (trade name, manufactured by Kyowa Chemical Co., Ltd.).

  As the silane coupling agent used for the treatment of the metal hydrate, those having a reactive group at the terminal are preferable. Examples of the silane coupling agent having a reactive group at the end include a silane coupling agent having a double bond such as a vinyl group at the end, and a silane coupling agent having an amino group or an epoxy group at the end. When performing surface treatment with a silane coupling agent, a silane coupling agent having a reactive group at the terminal may be used in combination with other silane coupling agents, or different reactions such as vinyl group, epoxy group, amino group, etc. Two or more silane coupling agents having a functional group at the end may be used in combination. An aliphatic surface treatment agent such as stearic acid may be used in combination.

  Examples of the silane coupling agent having a reactive group at the terminal include vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldimethoxysilane, and methacryloxy. Propyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N- (β-aminoethyl ) -Γ-aminopropyltripropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltripropyltrimethoxysilane, and the like. That.

  Two or more kinds of magnesium hydroxide surface-treated with the silane coupling agent may be used in combination, or mixed with magnesium hydroxide surface-treated with other treatment agents or untreated magnesium hydroxide. May be used.

  In the present invention, it is preferable to use magnesium hydroxide in which at least 50% or more of the metal hydrate used is surface-treated with a silane coupling agent, and more preferably at least 50% or more of the metal hydrate used is reactive. It is better to use magnesium hydroxide surface-treated with a silane coupling agent having a terminal group. Thereby, not only can the tensile strength of the flame retardant resin composition obtained and the wiring material coated with the resin composition be improved, but also a resin composition that does not deteriorate in mechanical properties even when a large amount of magnesium hydroxide is added. Can do. In addition, there are advantages such that the resin composition molded body is hardly damaged. Moreover, it is possible to significantly improve the low temperature resistance of the resin composition by using magnesium hydroxide surface-treated with a silane coupling agent having a reactive group at the terminal.

  Furthermore, by using 50% by mass or more of the magnesium hydroxide surface-treated with the reactive silane coupling agent, the moldability can be greatly improved, for example, the load during molding is reduced and the appearance is improved. I can do it. The process for improving the moldability is still unclear, but by using magnesium hydroxide that has been surface-treated with a reactive silane coupling agent, the crosslinking reaction that occurs when the organic peroxide described later is decomposed. As described above, it is considered that the crosslinking between the thermoplastic resin component and the magnesium hydroxide via the silane coupling agent is dominant, and the crosslinking between the thermoplastic resin components is suppressed. Furthermore, it is considered that the cross-linking bond between the thermoplastic resin component and the magnesium hydroxide via the silane coupling agent has a weaker interaction when the polymer is melted than the cross-linking bond between the thermoplastic resin components. Therefore, the load at the time of molding can be suppressed, and the appearance of the molded body can be kept good.

  The compounding quantity of the metal hydrate in this invention is 30-300 mass parts with respect to 100 weight part of thermoplastic resin components, Preferably it is 50-300 mass parts, More preferably, it is 70-280 mass parts. In order to acquire the said effect, it is preferable that the magnesium hydroxide processed with the reactive silane coupling agent is 50 mass% or more of the whole magnesium hydroxide. The amount of the reactive silane-treated magnesium hydroxide is 30 parts by mass or more, preferably 50 parts by mass or more, and more preferably 70 parts by mass or more with respect to 100 parts by mass of the polymer component.

  If the blending amount is too small, not only sufficient flame retardancy cannot be obtained, but the load during molding and the appearance of the molded product may be significantly reduced. If the blending amount is too large, not only the load during molding is remarkably increased, but also the mechanical strength may be significantly decreased.

  In the present invention, calcium carbonate can be added in place of the metal hydrate as long as the physical properties are not impaired. The compounding quantity is 0-100 mass parts with respect to 100 mass parts of resin components, More preferably, it is 0-60 mass parts.

  In this invention, in order to improve the dispersibility of the said metal hydrate, at least 1 sort (s) of fatty-acid metal salt chosen from zinc, magnesium, and calcium can be mix | blended as needed. Examples of the fatty acid of the fatty acid metal salt include oleic acid, lauric acid, myristic acid, palmitic acid, and stearic acid, and stearic acid is preferable.

(F) (Meth) acrylate-based and / or allylic crosslinking aid In the present invention, a (meth) acrylate-based and / or allylic crosslinking aid can be used as necessary.
Examples of the crosslinking aid used in the present invention include polyfunctional vinyl monomers such as divinylbenzene and triallyl cyanurate, or polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, Examples include polyfunctional (meth) acrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate. Specific examples include APG-200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

In a conventional method for producing a partially crosslinked resin compound in which a part of a resin is previously crosslinked and molding the compound, the use of a crosslinking aid is indispensable. Even if it is not used, it is possible to obtain a partially crosslinked resin molded product.
In addition, when a crosslinking aid is used, a uniform and efficient crosslinking reaction between the polymers due to the organic peroxide described later can be expected, and the polymers form a crosslinked bond via the crosslinking aid (normal crosslinking) Form). This bond strength is considered to be stronger than the cross-linking force between the polymer and magnesium hydroxide via the silane coupling agent described above, and depends on the molecular structure (straight chain length) of the cross-linking aid responsible for the bridge, By optimizing this, the heat resistance and mechanical strength of the molded body can be improved.

Furthermore, since the crosslinking aid does not react at the start of extrusion, it acts as a lubricant and can greatly reduce the extrusion load.
In particular, in the present invention, n = 2 to 16, more preferably n = 2 to 12, more preferably polypropylene glycol diacrylate (CH ₂ ═CHCOO— (C ₃ H ₆ O) _n —COCH═CH ₂ ) A diacrylate of n = 3 to 10 is preferable in terms of improving the heat resistance of the molded article, maintaining the mechanical strength and appearance, and moldability.

  The blending amount of the crosslinking aid used in the present invention is preferably in the range of 0 to 2.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin component. When a crosslinking aid is blended, a ratio of about 2 to 2.5 times the amount of organic peroxide added is preferable. When the blending amount of the crosslinking aid exceeds 2.0% by weight, crosslinking may proceed excessively and the extrusion load may be exceeded.

(G) Organic peroxide Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy). ) Hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) ) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert -Butyl peroxybenzoate, tert-butyl peroxy Propyl carbonate, diacetyl peroxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide and the like. Specifically, for example, Park Mill D, Perhexa 25B (trade name, manufactured by NOF Corporation) can be used.

Among these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane is most preferable in terms of odor and color.
The amount of peroxide added is preferably in the range of 0.02 to 1.0% by weight. If it is less than 0.02% by weight, the required crosslinking cannot be obtained. If it exceeds 1.0% by weight, extrusion molding becomes difficult and the appearance is remarkably deteriorated.

  Furthermore, the resin molded body of the present invention has various additives commonly used in electric wires, cables, cords, tubes, electric wire parts, sheets, etc., such as antioxidants, metal deactivators, difficulty A fuel (auxiliary) agent, a filler, a lubricant, an acid anhydride, a modified product thereof, and the like can be appropriately blended within a range that does not impair the object of the present invention.

  Antioxidants include amine-based antioxidants such as 4,4′-dioctyl diphenylamine, N, N′-diphenyl-p-phenylenediamine, and 2,2,4-trimethyl-1,2-dihydroquinoline polymer. Agent, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate , 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like, bis (2-methyl-4- ( 3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptoben ヅ imidazole and its zinc salt, pentaerythritol Lithol - tetrakis (3-lauryl - thiopropionate) and the like sulfur-based antioxidant such.

Examples of metal deactivators include N, N′-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.
In addition, flame retardants (auxiliaries) and fillers include carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compounds, quartz, talc, calcium carbonate, magnesium carbonate, boric acid. Examples include zinc, zinc stannate, white carbon, and melamine cyanurate.

  In particular, silicone compounds such as silicone rubber and silicone oil not only impart and improve flame retardancy, but also in insulators (coating layers comprising the flame retardant resin composition) and conductors in electric wires and cords. The cable has an effect of reducing trauma by controlling the adhesion force and imparting lubricity to the cable.

  Examples of the lubricant include hydrocarbons, fatty acids, fatty acid amides, esters, alcohols, and metal soaps.

Next, a method for producing a thermoplastic partially crosslinked resin molded product will be described.
In the present invention, the time of melt kneading means the time when each component is melted and kneaded by a Banbury mixer, and the time of molding means the time when the resin composition is put into a molding machine and molding is performed. .
In the resin molded product of the present invention, the components (a), (b), and (c) are crosslinked by the molding heat during molding due to the presence of the component (g).
Furthermore, by using magnesium hydroxide treated with a reactive silane coupling agent as magnesium hydroxide, (a), (b) and (c) components and reactive silane coupling agents are formed due to the presence of component (g). It reacts and crosslinks and becomes a cross-linked product having an interaction through magnesium hydroxide and a surface treatment agent. Even when a large amount of magnesium hydroxide is added due to this interaction, a high mechanical strength of the resin composition is maintained, and a resin composition having excellent wear resistance and being hardly scratched is obtained.

  In the method of finely crosslinking at the time of molding a molded body as in the present invention, for example, as compared with the case of molding using a compound that has been finely crosslinked in advance during melt-kneading as in Patent Documents 1 to 3, Can be set independently of the compound melt kneading conditions, and the load during molding can be greatly reduced, which greatly improves the degree of freedom in controlling the degree of crosslinking and the choice of resin that can be extruded. It becomes possible.

Hereinafter, the manufacturing method of the resin molding of this invention is demonstrated.
In the first embodiment of the method for producing a resin molded body in the present invention, the thermoplastic resin component contains 60 to 100% by mass of a resin and (d) 0 to 40% by mass of a plasticizer and / or oil , wherein (a), the ethylene-vinyl acetate copolymer of (b) and consists of at least one resin selected from the group consisting of (c), and at least the in thermoplastic resin component (a) containing more than 70 wt%, relative to the thermoplastic resin component 100 parts by mass, obtained by melt-kneading (e) 30 to 300 parts by weight, the resin composition containing 0 to 2.0 parts by weight (f) First step, second step of dispersing 0.02 to 1.0 part by mass of (g) in 100 parts by mass of thermoplastic resin component in the resin composition, and organic peroxide-dispersed resin composition, While heating above the peroxide decomposition temperature Consisting of a third step of molding.

In the first step, at least one resin selected from the group consisting of (a), (b) and (c), (d), (e) and (f) is melt-kneaded. The kneading temperature is preferably 160 ° C. or higher and 240 ° C. or lower. As a kneading method, any method usually used for rubber, plastic, etc. can be used satisfactorily. For example, a single screw extruder, a twin screw kneading extruder, a Banbury mixer, a kneader, a roll or the like is used. By this step, a composition in which each component is uniformly dispersed can be obtained.
If necessary, various additives such as a filler, an antioxidant, a light stabilizer, and a colorant may be added.

In the second step, the component (g) is dispersed in the resin. As the resin for dispersing the component (g), at least a part of the resin composition obtained in the first step may be used. For example, a master in which various additives such as a colorant are kneaded into a thermoplastic resin. Batches may be used. When using the resin composition obtained at the 1st process, it is preferable to disperse | distribute a component (g) in 25 to 100 mass% of the resin composition obtained at the 1st process.
The method for dispersing (g) is not particularly limited, and for example, a Henschel mixer can be used.
The treatment temperature in the second step is preferably 30 ° C. or higher and 60 ° C. or lower. If the organic peroxide is decomposed, crosslinking in the third step cannot be performed. Therefore, it is necessary to perform the treatment at a temperature at which the organic peroxide does not decompose.

In the third step, it was charged a dispersion of component (g) to the resin obtained in the resin composition obtained in the first step second step for forming shapes machine, by performing molding, desired A molded body can be obtained. Although it will not specifically limit as a molding machine if a desired molded object can be obtained, Extrusion molding, injection molding, press molding, etc. can be used suitably. The temperature of the molding process in the third step is 160 ° C. or higher and 240 ° C. or lower, preferably 180 ° C. or higher and 220 ° C. or lower.

Moreover, the 2nd form of the manufacturing method of the molded object in this invention is a thermoplastic resin component containing 60-100 mass% of resin and (d) plasticizer and / or 0-40 mass% of oil, and this resin is the (a), (b) Contact and (c) or Ranaru composed of at least one resin selected from the group and at least the ethylene-vinyl acetate copolymer of (a) in the thermoplastic resin component the polymer containing more than 70 wt%, relative to the thermoplastic resin to 100 parts by weight of the component, (e) 30 to 300 parts by weight of a metal hydrate, (f) (meth) acrylate and / or allyl type crosslinking aids After melt-kneading the composition containing 0 to 2.0 parts by weight of the agent to obtain a resin composition, 0.02 to 1.0 parts by weight of (g) with respect to 100 parts by weight of the thermoplastic resin component Disperse organic peroxide and at the same time organic peroxide It is characterized by molding while heating at a temperature above the side decomposition temperature.

In the second embodiment, as a means for obtaining the resin composition, the same method as in the first step in the first embodiment can be used.
The obtained resin composition and the organic peroxide are simultaneously charged into a molding machine. Although it will not specifically limit as a molding machine if a desired molded object can be obtained, Extrusion molding, injection molding, etc. can be used suitably. The temperature of the molding machine is 160 ° C. or higher and 240 ° C. or lower, preferably 180 ° C. or higher and 220 ° C. or lower.

  Immediately after being introduced into the molding machine, the temperature of the resin composition and the organic peroxide has not yet reached the decomposition temperature of the organic peroxide, so only the organic peroxide is dispersed in the resin composition. When the resin temperature gradually rises and reaches the decomposition temperature of the organic peroxide, since the organic peroxide is already uniformly dispersed in the resin, the partial cross-linking is uniformly performed throughout the resin composition. Then, it can shape | mold and can obtain a desired molded object.

  As a molded object of this invention, the electric wire and cable which have the molded object of this invention as a coating layer on the outer periphery of core materials, such as a conductor and an optical fiber, a code | cord | chord, a sheet | seat, a tube, etc. are mentioned, for example.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this.
Examples 1 to 8 are shown in Table 1, and Comparative Examples 1 to 7 are shown in Table 2.

<Examples 1-7, Comparative Examples 1-6>
Each component except the organic peroxide shown in Tables 1 and 2 was mixed, melt kneaded at 190 ° C. using a Banbury mixer, and pelletized after cooling. Thereafter, the obtained pellets and organic peroxide were mixed at room temperature with a Henschel mixer, and the resulting mixture was placed on a conductor (conducting tin-plated annealed copper stranded wire with a conductor diameter of 0.48 mmφ: 7 / 0.16 mmφ). The insulated wire was obtained by extrusion coating. The molding temperature was 190 ° C. The outer diameter of the obtained electric wire was 1.32 mm (the thickness of the coating layer was 0.42 mm).

<Example 8>
Each component except the organic peroxide shown in Table 1 was mixed, melt kneaded at 190 ° C. using a Banbury mixer, and pelletized after cooling. Then, the obtained pellets and organic peroxide were put into an extruder for electric wires, extrusion coated on a conductor (conducting tin plated annealed copper stranded wire with a conductor diameter of 0.48 mmφ: 7 / 0.16 mmφ), and insulated. I got an electric wire. The temperature of the molding machine was 190 ° C. The outer diameter of the obtained electric wire was 1.32 mm (the thickness of the coating layer was 0.42 mm).

<Comparative Example 7>
Each component shown in Table 2 Comparative Example 7 was blended and melt kneaded at 190 ° C. using a Banbury mixer to produce a resin composition. Next, using an extrusion coating apparatus for producing electric wires, an insulating resin composition previously melt-kneaded on a conductor (conducting tin plated annealed copper stranded wire with a conductor diameter of 0.48 mmφ: 7 / 0.16 mmφ) is extruded. The insulated wire was manufactured by covering with. The outer diameter was 1.32 mm (the thickness of the coating layer was 0.42 mm).

The following components were used for each component shown in the table. In addition, the number of each component in a table | surface is a mass part.
(01) Ethylene-vinyl acetate copolymer Revaprene VPKA8784 (trade name, manufactured by Bayer)
VA content 70% by weight
(02) Ternary copolymer acrylic rubber
Baymac GLS (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.)
(03) Maleic acid modified LLDPE
L-6100M (trade name, manufactured by JPO Corporation)
(04) Acrylic acid modified PP
P-1002 (trade name, manufactured by Crompton Co., Ltd.)
(05) Paraffinic oil
Diana Process PW90 (trade name, manufactured by Idemitsu Kosan Co., Ltd.)
(06) Silane coupling agent surface-treated magnesium hydroxide
Kisuma 5L (trade name, manufactured by Kyowa Chemical Co., Ltd.)
(07) Crosslinking aid
APG-200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(08) Organic peroxide
Perhexa 25B (trade name, manufactured by NOF Corporation)

The following tests were performed on each of the obtained insulated wires.
1) Tensile strength and elongation The tensile strength (MPa) and elongation (%) of each insulated wire were measured under the conditions of 25 mm between marked lines and a tensile speed of 500 mm / min. The UL required properties of elongation and tensile strength are respectively 150% or more and 10.3 MPa or more.
2) Heat deformation About each insulated wire, the heat deformation characteristic was performed at 136 degreeC according to UL1581 and the heat deformation test. The results are shown as a ratio (%) of deformation after heating with respect to before heating. When this value is 50% or more, it cannot be put to practical use.
3) Flame resistance (VW-1 standard)
Each insulated wire was subjected to UL 1581 Vertical Frame Test to indicate the number of passes (passed number / N number).
4) Formability The extrusion coating apparatus motor current value (A) when the screw rotation speed was 10 rpm when each insulated wire was manufactured was measured. A thing of 10 A or more cannot be put into practical use due to excessive load on the apparatus.

  From the results of the table, Examples 1 to 8 satisfy all the characteristics and an excellent insulated wire is obtained, whereas Comparative Example 1 in which a large amount of oil is blended is inferior in tensile strength, and magnesium hydroxide. Comparative Example 2 having too little results in poor tensile strength and flame retardancy. When there is too much magnesium hydroxide (Comparative Example 3), the elongation is not satisfied, and when there is too much crosslinking aid (Comparative Example 4), the elongation is small. When the amount of organic peroxide is too small (Comparative Example 5), the tensile strength and heat deformability are inferior. On the other hand, when the amount is too large (Comparative Example 6), the crosslinking proceeds too much, resulting in poor elongation. . Moreover, since the extrusion load is too high, the comparative example 7 by which bridge | crosslinking is performed at the time of kneading | mixing has resulted in inferior workability.

As described above, the production method of the present invention can obtain a thermoplastic partially crosslinked resin molded article without requiring special equipment for extrusion molding by performing partial crosslinking simultaneously with molding at the time of resin molding. It is a manufacturing method.
Furthermore, the production method of the present invention is a method for producing an excellent thermoplastic partially crosslinked resin molded article having a low load during molding and high mass productivity.

Claims (6)

The thermoplastic resin component contains 60 to 100% by mass of resin and (d) 0 to 40% by mass of plasticizer and / or oil, and the resin is (a) polyethylene, polypropylene, ethylene / α-olefin copolymer, ethylene A polyolefin resin selected from vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer, ethylene / (meth) acrylic acid copolymer and binary or ternary copolymer acrylic rubber; b) Polyethylene, polypropylene, ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer and ethylene / (meth) modified with unsaturated carboxylic acid or derivatives thereof A polymer selected from acrylic acid copolymers, and (c) a group of styrenic elastomers. It is, and with respect to at least the ethylene-vinyl acetate copolymer (a) contains more than 70 wt%, the thermoplastic resin to 100 parts by weight of the component in the thermoplastic resin component, (e) a metal hydrate A first step of melt-kneading a mixture containing 30 to 300 parts by mass, (f) (meth) acrylate-based and / or allylic crosslinking aid 0 to 2.0 parts by mass to obtain a resin composition, and the heat In the first step and the second step, 0.02 to 1.0 part by weight of the organic peroxide (g) is dispersed in the resin at a temperature at which it does not decompose with respect to 100 parts by weight of the plastic resin component. A method for producing a thermoplastic partially crosslinked resin molded article, comprising a third step of molding and crosslinking the obtained resin composition while heating at an organic peroxide decomposition temperature or higher. The thermoplastic resin component contains 60 to 100% by mass of resin and (d) 0 to 40% by mass of plasticizer and / or oil, and the resin is (a) polyethylene, polypropylene, ethylene / α-olefin copolymer, ethylene A polyolefin resin selected from vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer, ethylene / (meth) acrylic acid copolymer and binary or ternary copolymer acrylic rubber; b) Polyethylene, polypropylene, ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer and ethylene / (meth) modified with unsaturated carboxylic acid or derivatives thereof A polymer selected from acrylic acid copolymers, and (c) a group of styrenic elastomers. It consists at least in one resin, and at least the ethylene-vinyl acetate copolymer (a) contains more than 70 mass% in the thermoplastic resin component, relative to the thermoplastic resin 100 parts by weight of component (E) 30 to 300 parts by mass of a metal hydrate, (f) a composition containing 0 to 2.0 parts by mass of a (meth) acrylate-based and / or allylic crosslinking aid is melt-kneaded to obtain a resin composition After obtaining the product, 0.02 to 1.0 part by mass of (g) the organic peroxide is dispersed with respect to 100 parts by mass of the thermoplastic resin component, and at the same time, it is molded while being heated at the organic peroxide decomposition temperature or higher. And a method for producing a thermoplastic partially crosslinked resin molded article.   3. The method for producing a thermoplastic partially crosslinked resin molded article according to claim 1, wherein 50% by mass or more of the metal hydrate is treated with a silane coupling agent.   The said silane coupling agent has a reactive group in the terminal, The manufacturing method of the thermoplastic partially crosslinked resin molding of Claim 3 characterized by the above-mentioned.   The method for producing a thermoplastic partially crosslinked resin molded article according to any one of claims 1 to 4, wherein the metal hydrate is magnesium hydroxide. The method for producing a thermoplastic partially crosslinked resin molded article according to any one of claims 1 to 5, wherein the thermoplastic partially crosslinked resin molded article is molded by extrusion molding.