JP2018083887A - Master batch resin composition for resin foam compact and production method thereof and resin foam compact obtained by processing the same and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a master batch resin composition for resin foam compacts that has high deodorant effect and is also free from safety problems and a production method thereof and resin foam compacts obtained by processing the same and a production method thereof.SOLUTION: A master batch resin composition of the present invention includes a base resin that can be melted by heating and a deodorant, the deodorant is at least one selected from zinc sulfate and cupric sulfate, and gets rid of odor due to decomposition of a chemical foaming agent and a crosslinking agent. When the master batch resin composition is formed into a foam forming resin composition by kneading the foam forming resin with a chemical foaming agent and a crosslinking agent, a deodorant effect is provided for both of an odor due to decomposition of the chemical foaming agent and crosslinking agent during production of the resin foam compacts and odor derived from odor generating material attached to the compacts.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a masterbatch resin composition for foam molded articles, a method for producing the same, a resin foam molded article obtained by processing the same, and a method for producing the same.

  Conventionally, various compositions in which an inorganic salt or the like is mixed with a resin have been proposed. For example, Patent Documents 1 to 3 propose a method in which a resin is melt-kneaded and mixed with an inorganic salt to form a composition. Patent Document 4 proposes that a zinc oxide powder having a specific particle diameter is kneaded into a thermoplastic fiber such as polyester or nylon. Patent Document 5 proposes to suppress ammonia odor generated from a chemical foaming agent during foam molding with aluminum powder.

Japanese Patent Laid-Open No. 5-230325 JP 2006-225550 A JP-A-1-263130 Japanese Patent No. 4228856 JP 2003-292661 A

However, when producing resin foam, it is difficult to efficiently suppress ammonia-like odors such as ammonia, low molecular amine odor, or phenylamine odor generated from chemical foaming agents in the prior art. Powder has safety problems, and it has been required to solve these problems.
On the other hand, a crosslinking agent is added when producing the resin foam. In particular, organic peroxides used for rubber and polyolefin crosslinkers are bonded to carbon in saturated bonds by generating free radicals by breaking peroxide bonds in the chemical structure by heating and kneading with resin. Extract hydrogen and generate new radicals. It is said that these generated radicals recombine and form a bridge between saturated compounds to reinforce the resin. However, when this organic peroxide generates free radicals by heating and kneading with a resin, a by-product odor generated by this decomposition has been a problem.

  In order to solve the above-mentioned conventional problems, the present invention provides a masterbatch resin composition for a resin foam molded article having a high deodorizing effect and no safety problem, a method for producing the same, and a resin foam molded article obtained by processing the same. A manufacturing method thereof is provided.

  The masterbatch resin composition for resin foam moldings of the present invention is a masterbatch resin composition containing a heat-meltable base resin and a deodorizer, wherein the deodorizer comprises zinc sulfate and cupric sulfate. It is at least one selected from the group consisting of deodorizing odor caused by decomposition of the chemical foaming agent and the crosslinking agent.

  The method for producing a masterbatch resin composition for resin foam moldings according to the present invention is a method for producing the above masterbatch resin composition for resin foam moldings, comprising a resin melting part and a kneading and dispersing part provided with a decompression line And continuously connecting the extruding part, supplying to the kneading and dispersing part at least one deodorant selected from zinc sulfate and cupric sulfate dissolved in a solvent, and a resin melted by heating, Simultaneously with mixing, the solvent is removed in a gaseous state from the reduced pressure line, and then the resin composition is extruded from the extrusion part.

  The resin foam molded article of the present invention is a resin foam molded article obtained by mixing and crosslinking a foam molding resin and a resin batch molding masterbatch resin composition containing a deodorant, wherein the resin foam molded article comprises: It contains at least one deodorant selected from zinc sulfate and cupric sulfate, and includes a bubble portion resulting from a chemical foaming agent.

  The method for producing a resin foam molded article of the present invention is a method for producing the resin foam molded article, wherein the master batch resin composition for resin foam molding includes a foam molding resin, a deodorant, and a crosslinking agent. And a chemical foaming agent are melt-kneaded and reacted with a crosslinking agent and a chemical foaming agent to crosslink and foam.

  The present invention provides a resin foam molded article having a high deodorizing effect and no safety problem by containing at least one deodorant selected from zinc sulfate and cupric sulfate in the resin foam molded article. it can. The deodorizing effect is due to the odor caused by the decomposition of the chemical foaming agent during the production of the resin foam molded article, the odor caused by the by-product due to the decomposition of the crosslinking agent such as organic peroxide, and the odor generation product adhering to the molded article. Any of the odors caused by

FIG. 1 is a schematic explanatory view of an extruder used in one embodiment of the present invention.

  The present invention is a masterbatch resin composition comprising a heat-meltable base resin and a deodorant, wherein the deodorant is at least one selected from zinc sulfate and cupric sulfate, and chemical foaming The odor resulting from the decomposition of the agent and the crosslinking agent is deodorized. This masterbatch resin composition is obtained by foaming a resin composition containing a chemical foaming agent, a crosslinking agent, and at least one deodorant selected from zinc sulfate and cupric sulfate to a foam molding resin. Applicable. A preferred deodorant is zinc sulfate. The deodorant is preferably finely dispersed in the resin. Preferably, no deodorant particles having a particle size of 100 nm or more are present. The state where there is no particle having a particle size of 100 nm or more can be confirmed by observing with a scanning electron microscope (SEM) that no particle is seen. In order to obtain such a state, a deodorant dissolved in a solvent is used and is added to the resin by liquid addition.

  The deodorant is preferably mixed in an amount of 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin composition. Part. If it is said addition amount, the effect of deodorizing etc. is also high and it will be easy to perform a shaping process.

  The resin used is preferably a thermoplastic resin. Examples of the thermoplastic resin include polyolefins such as polypropylene and polyethylene, polyamides such as polyoxymethylene and nylon, polycarbonates, polyvinyl chloride, ABS resins, AS resins, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and thermoplastic elastomers. is there. Among these, polyolefin resins are preferable.

  Examples of the polyolefin resin include homopolymers of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene, and butene-1, α-olefins and ethylene, propylene, butene-1, and 3-methylbutene-1. , Pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, etc., other α-olefins having about 2 to 20 carbon atoms, vinyl acetate, acrylic acid, methacrylic acid, acrylic acid Specific examples of such copolymers include branched ethylene homopolymers such as low / medium / high-density polyethylene, linear ethylene homopolymers, and ethylene-propylene copolymers. Polymer, ethylene-butene-1 copolymer, ethylene-4-methylpentene-1 copolymer, ethylene-hexene-1 copolymer, ethylene -Octene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, Ethylene-propyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-hexyl acrylate copolymer, ethylene-octyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate A copolymer, an ethylene-propyl methacrylate copolymer, an ethylene-butyl methacrylate copolymer, an ethylene-hexyl methacrylate copolymer, an ethylene resin such as an ethylene-octyl methacrylate copolymer; a propylene homopolymer, Propylene-ethylene copolymer, propylene-ethylene- Propylene resin Ten -1 copolymer; butene-1 homopolymer, butene-1-ethylene copolymer, butene-1-based resins such butene-1-propylene copolymer, and the like. Among these, a polyethylene resin is preferable, and a (linear) low density polyethylene resin is more preferable. Since this resin is soft and easy to process, it is suitable for a foam molded article.

  Such a masterbatch resin composition uses an extruder, continuously connected to an extrusion section to a kneading chamber equipped with a decompression line, and in the kneading chamber, a deodorant dissolved in a solvent, The resin obtained by heating and melting is supplied, and simultaneously with mixing, the solvent is removed in a gaseous state from the decompression line, and then the resin composition is extruded from the extrusion part.

  Hereinafter, the manufacturing method of a masterbatch resin composition is demonstrated using drawing. FIG. 1 is a schematic explanatory view of an extruder used in one embodiment of the present invention. The extruder 1 includes a raw material supply port 2, a resin melting part 3, a kneading and dispersing part 4, a decompression line 5, an extrusion part 6, and a take-out part 7. First, a deodorant dissolved in polymer and water is supplied from the raw material supply port 2 of the resin melting part 3. You may mix both before supply. Next, the mixture is fed to the kneading / dispersing section 4, and a plurality of kneading plates are rotating in the kneading / dispersing section 4, where the polymer and the compound dissolved in water are uniformly mixed. Next, moisture is removed from the decompression line 5 in the state of water vapor. Next, the resin composition is extruded from the extrusion unit 6, cooled, and taken out from the take-out unit 7. If it cuts after cooling, it will become a pellet-shaped resin composition.

  The obtained masterbatch resin composition can be made into a resin foam molded article blended with a foam molding resin and subjected to foam molding. The resin foam molding is obtained by kneading the resin for foam molding, the masterbatch resin composition for resin foam molding containing a deodorizer, a crosslinking agent, and a chemical foaming agent using an extruder. By reacting an agent and a chemical foaming agent, a crosslinked and foamed resin molded body is obtained. At this time, cross-linking due to the cross-linking agent (cross-linking reaction) and bubbles due to the foaming agent are formed, while the odor generated by decomposition of the cross-linking agent and the foaming agent is added to the masterbatch resin composition Deodorized by at least one deodorant selected from zinc sulfate and cupric sulfate.

  Examples of the chemical foaming agent include benzenesulfonyl hydrazide, benzene-1,3-sulfonyl hydrazide, diphenylsulfone-3,3′-disulfonyl hydrazide, diphenyl oxide-4,4′-disulfonyl hydrazide, p, p′-. Sulfonyl hydrazide compounds such as oxybisbenzenesulfonyl hydrazide (OBSH), paratoluenesulfonyl hydrazide; azo compounds such as azodicarbonamide, 2,2′-azobisisobutyronitrile, azohexahydrobenzonitrile, diazoaminobenzene, etc. Can be mentioned. Among these, since it becomes a polyolefin resin composition for foam molding that is extremely excellent in the foaming efficiency, p, p′-oxybisbenzenesulfonylhydrazide (azodicarbonamide alone or a mixture of OBSH and azodicarbonamide) Hereinafter, this is referred to as OBSH.)

  Examples of the crosslinking agent include organic peroxides such as peroxyketals, dialkyl peroxides, diacyl peroxides, and peroxy esters. Among these, dialkyl peroxides represented by the following chemical formulas (1) to (3) are preferable.

  The resin foam molding may be an independent foam or a continuous foam. In the case of sheet molding, a closed foam molded body is obtained by foaming after sheet molding. In the above, a continuous foamed molded product is obtained by applying mechanical deformation after foaming.

  In order to obtain the resin foam molded article of the present invention, for example, referring to Japanese Patent Publication No. 1-444499, a deodorant was blended with a polyethylene resin and melt-kneaded to form particles, pellets, etc. A resin compound (so-called master batch) is used. Next, this resin compound, chemical foaming agent, and crosslinking agents such as organic peroxides are mixed into the base thermoplastic resin, and foaming aids are melt-kneaded with a mixing roll, etc., if necessary. A resin composition is used. Then, the resin composition for foam molding is put into a predetermined mold, taken out after being heated under pressure by a press, inserted into a non-hermetic open / close mold, kept at the foaming temperature, and a closed-cell foamed molding. And Furthermore, a continuous foamed molded product in which the bubble film is ruptured by compressing and deforming with two constant-velocity rolls to make the bubbles communicated. At this time, foaming may be performed simultaneously with melt kneading, or foaming may be performed in a separate process. . In the case of foaming simultaneously with melt-kneading, it is suitable for a sheet form. When foaming is performed in a separate process, it is suitable for forming foamed resin molded products having various shapes.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. In addition, when the addition amount is simply expressed as% in the following examples, it means mass%.

(Measuring method)
<Observation of inorganic salt functional agent particles>
The cross section of the polymer was evaluated by observation with a scanning electron microscope (SEM) and magnification set appropriately. Evaluation was performed according to the following criteria.
A: State in which particles are not seen, that is, state in which there are no particles having a particle size of 100 nm or more B: State in which particles are seen <deodorant>
(1) Deodorizing property at the time of manufacturing a resin foam molded article The odor in the field in the extrusion process at the time of manufacturing a foam molded article was evaluated according to the following criteria.
○: No odor in process (complex odor such as ammonia-like odor or by-product) ×: There is odor in process

<Common operation>
(1) An aqueous solution in which a deodorant was dissolved was prepared.
(2) About half of the resin was ground to 1 mm or less. The remainder was supplied with the polymer and the deodorant dissolved in water from the raw material supply port 2 of the extruder shown in FIG. 1 with the pellets (cylindrical shape having a diameter of 2 mm and a height of 2 mm).
(3) In the resin melting section 2, the feed is fed forward along the rotation axis, and in the kneading and dispersing section 4, a plurality of kneading plates are rotated, where the deodorant dissolved in the polymer and water is uniform. Then, the water was removed at the same time by setting the vacuum line 5 to a vacuum (negative pressure).
(4) Next, the resin composition was extruded from the extrusion portion 6, cooled and taken out from the takeout port 7.
(5) It led to the pelletizer and pelletized.
(6) The processing temperature in the extruder is 150 to 160 ° C. for polyethylene (PE).

Example 1
A linear low density polyethylene resin is used as a base resin, and 10 parts by mass of a deodorant (active ingredient 3%) made of fine zinc sulfate with a maximum particle size of 100 nm or less is added to 100 parts by mass of the base resin and mixed. 1 was melt kneaded with an extruder shown in FIG. The polymer extruded from the extruder was cooled and cut to form a cylindrical deodorant mixed pellet (resin compound) having a diameter of 2.5 mm and a length of 3.0 mm.

  16 parts by mass of azodicarbonamide as a chemical foaming agent and 1 part by mass of dicumyl peroxide represented by the above formula (3) as a crosslinking agent with respect to 100 parts by mass of a linear low density polyethylene resin, and the deodorant mixture 5 parts by mass of the pellets were added, melted and kneaded with an extruder, and simultaneously sheet foamed. The obtained resin foam sheet was a closed cell. About 1003% by mass of the obtained resin foam sheet contained about 0.013% by mass of zinc sulfate as a deodorant. The observation result of the particle | grains by SEM of the obtained resin foam sheet was A, and the deodorizing property at the time of molded object manufacture was (circle).

(Example 2)
The same operation as in Example 1 was performed except that 10 parts by mass of the deodorant mixed polymer particles were added. About 100% by mass of the obtained resin foam sheet, zinc sulfate was contained as a deodorant in an amount of about 0.025% by mass. The observation result of the particle | grains by SEM was A, and the deodorizing property at the time of molded object manufacture was (circle).

(Example 3)
The same operation as in Example 1 was performed except that 20 parts by mass of the deodorant mixed polymer particles were added. About 100% by mass of the obtained resin foam sheet contained about 0.045% by mass of zinc sulfate as a deodorant. The observation result of the particle | grains by SEM was A, and the deodorizing property at the time of molded object manufacture was (circle).

(Comparative Example 1)
The same procedure as in Example 1 was performed except that the deodorant mixed polymer particles were not added. The deodorizing property during the production of the molded product was x.

  The resin composition of the present invention can be applied to various resin foams such as a heat insulating material, a sound absorbing material, a buoyancy material, an elastic material, a lightweight material, and a sealing material. Moreover, a molded object can also be shape | molded in various shapes.

1 Extruder 2 Raw Material Supply Port 3 Resin Melting Portion 4 Kneading Dispersion Portion 5 Decompression Line 6 Extrusion Portion 7 Extraction Portion

Claims (7)

A masterbatch resin composition comprising a heat-meltable base resin and a deodorant,
The deodorizer is at least one selected from zinc sulfate and cupric sulfate, and deodorizes the odor caused by the decomposition of the chemical foaming agent and the crosslinking agent. Resin composition.   The master batch resin composition for resin foam molding according to claim 1, wherein the deodorizer has a particle size of less than 100 nm and is dispersed in the resin.   The master batch resin composition for resin foam molded articles according to claim 1 or 2, wherein the deodorizer is blended in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin. It is a manufacturing method of the masterbatch resin composition for resin foam moldings in any one of Claims 1-3,
Continuously connecting the resin melting part, the kneading dispersion part equipped with a decompression line, and the extrusion part,
At least one deodorant selected from zinc sulfate and cupric sulfate dissolved in a solvent and a heat-melted resin are supplied to the kneading dispersion part, and simultaneously with mixing, the solvent is removed from the pressure reduction line with gas. The method for producing a masterbatch resin composition for a resin foam molded article, characterized in that the resin composition is removed in a state and then the resin composition is extruded from an extruded portion.   A resin foam molded article obtained by mixing and crosslinking a foam molding resin and a resin batch molding masterbatch resin composition containing a deodorant, wherein the resin foam molded article comprises zinc sulfate and cupric sulfate. A resin foam-molded article comprising at least one deodorant selected and including a cell part resulting from a chemical foaming agent.   The resin foam molded body according to claim 5, wherein the resin foam molded body is independent foam. It is a manufacturing method of the resin foam molding according to claim 5 or 6,
The resin composition for foam molding, the masterbatch resin composition for foam molding including a deodorizer, the cross-linking agent, and the chemical foaming agent are melt-kneaded, and the cross-linking agent and the chemical foaming agent are reacted to crosslink. A method for producing a resin foam molded article, characterized in that the foamed foam is made into a foam.

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