Resin molded product

Abstract

A resin molded product having a polyolefin-based polymer resin layer 1 containing an ammonium salt of an aromatic monocarboxylic acid as specified below having an average particle size of 20 µm or more and a sodium salt or potassium salt of a carboxylic acid, wherein one or more kinds of the ammonium salt selected from ammonium salts of benzoic acid, aminobenzoic acid, salicylic acid, p-tert-butylbenzoic acid, o-sulfobenzoic acid, 1-naphthoic acid and 2-naphthoic acid may be contained.

Description

Technical area

[0001] The present invention relates to a resin molded product. State of the art

[0002] As described in Patent Literature 1, corrosion inhibitor compositions each containing a volatile corrosion inhibitor in the form of alkylammonium salt of dicarboxylic acid and a water-soluble corrosion inhibitor, and corrosion inhibitor resin compositions each made of a thermoplastic resin containing such a corrosion inhibitor composition are known.

[0003] Furthermore, as described in Patent Literature 2, packaging containers for metal products each made of a multilayer film consisting of a base resin film directly bonded to a film containing a volatile corrosion inhibitor by thermal lamination and then post-formed so that the resin film containing the volatile corrosion inhibitor faces the metal product side are known.

[0004] Patent Literature 3 discloses a rust-preventive film containing a rust-preventive agent in a polyolefin resin-containing film or on a surface thereof, the rust-preventive film having a haze of 20-50% and a thickness of 20-100 μm, and containing at least one of nitrites, amine compounds, fatty acid compounds, and aromatic fatty acid compounds as the rust-preventive agent. Patent Literature 4 discloses silicone resin compounds prepared by blending a siloxane resin, a filler, and an alkali metal salt selected from the group consisting of an alkali metal carbonate plus a carboxylic acid, an alkali metal bicarbonate plus a carboxylic acid, an alkali metal carbonate plus an ammonium salt of a carboxylic acid, an alkali metal bicarbonate plus an ammonium salt of a carboxylic acid, an alkali metal salt of a carboxylic acid, and mixtures thereof.Patent Literature 5 discloses a rust-preventive film containing a thermoplastic resin and an amine salt of a dicarboxylic acid, a metal salt of a chain or cyclic aliphatic dicarboxylic acid, and a metal salt of an aromatic monocarboxylic acid. Patent Literature 6 discloses cable sheathing material consisting of the following raw materials in parts by weight: 40-65 parts of chlorosulfonated polyethylene, 22-40 parts of polytetrafluoroethylene, 12-18 parts of butadiene-styrene-divinylbenzene polymer, 1-3 parts of octadecyl acrylate, 2-6 parts of bis(2-butoxyethyl) ether, 0.6-1.8 parts of ammonium benzoate, 0.4-2.6 parts of 1,3-phenylenediamine-4-sulfonic acid, 1-5 parts of pentaerythritol diphosphite distearate, 2-3 parts of 1,4-butane sultone, 1-2 parts of tert-butyldimethylsilyl chloride, 0.4-0.9 parts of n-propylamine, 4-9 parts of calcium stearate, 1-3 parts of barium stearate, 1.3-2.4 parts 1,2-epoxyoctane, 4-10 parts nano-silica and 5-12 parts calcium silicate. State of the art literaturePatent literature Patent literature 1: JP 2007 - 308 726 A Patent literature 2: JP 2007 - 230 568 A Patent literature 3: JP 2011 - 195 602 A Patent Literature 4: US 5,026,811 A Patent literature 5: JP 2013 - 007 072 A Patent Literature 6: CN 1 05 860 303 A Summary of the inventionProblems to be solved by the invention

[0005] The use of a two-layer laminated film as an anti-corrosive film for storing metal products, etc., contributes to a longer anti-corrosive effect of the film; however, when an anti-corrosive film with a resin layer containing a volatile corrosion inhibitor and a water-soluble corrosion inhibitor is used, for example, according to the invention described in Patent Literature 1, it becomes difficult to control the release of the liquid corrosion inhibitor during use, thereby making it difficult to produce the corrosion inhibitor for a long period of time.

[0006] As described in Patent Literature 2, covering one side of a film containing a volatile corrosion inhibitor with a base material film is known as a way to maintain the anticorrosive effect longer.

[0007] However, these films are not able to maintain their anti-corrosive properties over a long period of time, and there is now a need to achieve long-term anti-corrosive effects for a wide range of products such as cast iron, steel sheets and galvanized steel sheets. Means to solve the problems

[0008] The inventor of the present invention studied seriously to solve the above problems and made the present invention after finding that it could be solved by the following means: 1. A resin molded product comprising a polyolefin-based polymer resin layer 1 containing an ammonium salt of an aromatic monocarboxylic acid as specified below having an average particle size of 20 μm or more and a sodium salt or potassium salt of a carboxylic acid, wherein one or more kinds of the ammonium salt selected from ammonium salts of benzoic acid, aminobenzoic acid, salicylic acid, p-tert-butylbenzoic acid, o-sulfobenzoic acid, 1-naphthoic acid and 2-naphthoic acid may be contained. 2. The resin molded product according to 1, wherein the resin layer 1 contains one or more kinds of substances selected from carboxylic acid, benzotriazole compound and tolyltriazole compound. 3. The resin molded product according to 1 or 2, which is further covered with a base material layer. 4. The resin molded product according to 3, wherein the base material layer contains one or more kinds of substances selected from metal salt of nitrous acid, carboxylic acid, benzotriazole compound, tolyltriazole compound and metal salt of carboxylic acid. 5. The resin molded product according to any one of 1 to 4, which is a sheet-like article or a bag-like article. Effects of the invention

[0009] According to the resin molded product containing a specific ammonium salt of carboxylic acid with a specific particle size, as proposed by the present invention, a container, a film-like article, or a bag-like article composed at least partially of this molded product can maintain a corrosion protection effect for a long period of time when used for storing metal products or other products susceptible to corrosion, or when packaged together with such products. This enables reliable and long-term corrosion inhibition of metal products during transportation, storage, etc. Mode for carrying out the invention

[0010] The present invention is a resin molded product comprising a resin layer 1, and the invention also allows the provision of a resin layer 2 and, depending on the situation, a base material layer.

[0011] The modes of the present invention are explained below. (ammonium salt of aromatic monocarboxylic acid)

[0012] The ammonium salts of aromatic monocarboxylic acids used include ammonium salts of benzoic acid, aminobenzoic acid, salicylic acid, p-tert-butylbenzoic acid, o-sulfobenzoic acid, 1-naphthoic acid and 2-naphthoic acid, of which one or more types may be used.

[0013] The use according to the invention of an ammonium salt of certain aromatic monocarboxylic acids, particularly when the molded product has only the resin layer 1, includes the aspect of achieving a corrosion protection property over a long period of time.

[0014] Furthermore, the use of an ammonium salt of certain aromatic monocarboxylic acids according to the invention is advantageous in terms of the appearance of the product, since some ammonium salts of aliphatic carboxylic acids would bleed onto the surface of the resin molded product and thereby impair the appearance of the product.

[0015] The content of the aromatic ammonium salt of monocarboxylic acid is preferably 0.01 to 10 parts by weight, or more preferably 0.1 to 9 parts by weight, or even more preferably 0.2 to 6 parts by weight, based on 100 parts by weight of the resin layer in which it is contained. If the content is less than 0.01 part by weight, it becomes difficult to achieve sufficient anti-corrosive properties, while a content of more than 10 parts by weight makes molding difficult.

[0016] The ammonium salt of aromatic monocarboxylic acid is contained in the resin layer 1 in the form of particles, and their average particle size is 20 μm or more, or more preferably 20 to 400 μm, or even more preferably 20 to 200 μm, or particularly preferably 20 to 100 μm. It should be noted that this average particle size is obtained based on the long diameters of the particles of the ammonium salt of aromatic monocarboxylic acid contained in the resin layer, excluding particles whose long diameter is 10 μm or less. This is because fine particles may not contribute much to the long-term maintenance of the anti-corrosive property, which means that such fine particles are present in a small number or that particles of a certain size range are contained in a large number.

[0017] In addition, the maximum particle size of the aromatic monocarboxylic acid ammonium salt contained in the resin layer 1 is preferably 5000 μm or less, or more preferably 3000 μm or less, or even more preferably 500 μm or less. If the particle size of the aromatic monocarboxylic acid ammonium salt exceeds 5000 μm, the strength of the resin molded product may decrease, or the metal product may be contaminated by falling out of particles, etc. The maximum particle size represents the largest particle size among the particle sizes measured on 1000 particles.

[0018] As long as the average particle size and / or the maximum particle size are within the aforementioned ranges, the aromatic monocarboxylic acid ammonium salt particles, in a resin-coated state, form convex portions on the surface of the resin layer 1. The presence of these convex portions enables the generation of more corrosion-inhibiting gas, which contributes to improving the anti-corrosive property. Furthermore, these convex portions on the film surface prevent the film from adhering to the object to be protected from corrosion and prevent the aromatic monocarboxylic acid ammonium salt particles from directly contacting the object and thereby contaminating the surface of the object.

[0019] However, a series of steps from compounding aromatic monocarboxylic acid ammonium salt particles into a resin forming the resin layer, to melting / kneading the resin, to forming a film, for example, may crush the carboxylic acid ammonium salt powder and cause its average particle size to decrease compared to the size before compounding. For this reason, the aforementioned average particle size according to the present invention is a value related to the aromatic monocarboxylic acid ammonium salt contained in the resin layer 1 after the resin layer 1 is formed.

[0020] When an ammonium salt of aromatic monocarboxylic acid with these specific particle sizes is included, the anti-corrosive effect can be stably maintained over a long period of time because the amount of anti-corrosive gas generated is controlled. (sodium salt or potassium salt of carboxylic acid)

[0021] The sodium salt or potassium salt of carboxylic acid according to the present invention is a sodium salt or potassium salt of aliphatic carboxylic acid or of aromatic carboxylic acid.

[0022] Sodium salts or potassium salts of carboxylic acids of these types include sodium salts or potassium salts of aliphatic carboxylic acids such as isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid, oleic acid, isohexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, isoheptic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, issoundecanoic acid, isododecanoic acid, 2-butyloctanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedioic acid, and the like, as well as aromatic carboxylic acids such as benzoic acid, Aminobenzoic acid, salicylic acid, p-tert-butylbenzoic acid, o-sulfobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid and the like,one or more of these can be used.

[0023] The content of the sodium salt or potassium salt of carboxylic acid is preferably 0.001 to 10 parts by weight, or more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the resin layer in which it is contained. If the content is less than 0.001 part by weight, it becomes difficult to achieve sufficient anti-corrosive properties, while a content of more than 10 parts by weight not only makes molding difficult but also makes it difficult to achieve long-term anti-corrosive properties. (carboxylic acid)

[0024] The carboxylic acid according to the present invention may be an aliphatic carboxylic acid or an aromatic carboxylic acid.

[0025] Carboxylic acids of these types include isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid, oleic acid, isohexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, isoheptic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, issoundecanoic acid, isododecanoic acid, 2-butyloctanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedioic acid, and other aliphatic carboxylic acids, as well as benzoic acid, aminobenzoic acid, salicylic acid, p-tert-butylbenzoic acid, o-Sulfobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid and other aromatic carboxylic acids, one or more of which may be used.

[0026] The content of such a carboxylic acid is preferably 0.001 to 10 parts by weight, or more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the resin layer in which it is contained. If the content is less than 0.001 parts by weight, further improvement of the anti-corrosive property becomes difficult, while a content of more than 10 parts by weight not only makes molding difficult but also makes it difficult to realize long-term anti-corrosive property. (Benzotriazole-based compound and tolyltriazole-based compound)

[0027] As the benzotriazole-based compound and tolyltriazole-based compound according to the present invention, one or more kinds selected from benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, etc. can be used.

[0028] The content of such a benzotriazole-based compound and a tolyltriazole-based compound is preferably 0.001 to 10 parts by weight, or more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the resin layer in which it is contained. If the content is less than 0.001 part by weight, further improvement of the long-term anti-corrosive property becomes difficult, while a content of more than 10 parts by weight not only makes molding difficult but also makes it difficult to realize the long-term anti-corrosive property. (metal salt of nitrous acid)

[0029] As the metal salt of nitrous acid according to the present invention, one or more kinds selected from sodium salt, potassium salt, calcium salt, magnesium salt, etc., of nitrous acids can be used.

[0030] The content of such a metal salt of nitrous acid is preferably 0.001 to 10 parts by weight, or more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the resin layer in which it is contained. If the content is less than 0.001 parts by weight, further improvement of the anti-corrosive property becomes difficult, while a content of more than 10 parts by weight not only makes molding difficult but also makes it difficult to realize long-term anti-corrosive property. (Resin layers 1 and 2)

[0031] As the resin constituting each of the resin layers 1, 2, one or more types selected from polymers based on polyolefin or, in particular, olefin homo- and / or copolymers with olefin monomers may be selected and used independently for each layer.

[0032] Olefins (olefin monomers) that make up these polyolefin-based polymers include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc. Accordingly, polyolefin-based polymers include ethylene-based polymers, propylene-based polymers, 1-butene-based polymers, 1-hexene-based polymers, 4-methyl-1-pentene-based polymers, etc. Each of these types of polymers can be used individually, or two or more types can be combined. In other words, a polyolefin-based polymer can be a mixture of different types of polymers.

[0033] Of the above, ethylene-based polymers include ethylene homopolymers (polyethylene) and copolymers of ethylene and other monomers (ethylene copolymers). Ethylene homopolymers include, for example, low-density polyethylene (LDPE), linear low-density polyethylene (L-LDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).

[0034] Furthermore, ethylene copolymers include ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-pentene copolymers, ethylene / 1-hexene copolymers, ethylene / 1-octene copolymers, ethylene / 4-methyl-1-pentene copolymers, etc.

[0035] It should be noted that the ethylene units (component units derived from ethylene) contained in the ethylene copolymer need only account for more than 50% (usually up to 99.999%) of all component units, but may, for example, account for 80 to 99.999% or 90 to 99.995% or even 99.0 to 99.990% of all component units.

[0036] Furthermore, propylene-based polymers include propylene homopolymers (polypropylenes) and copolymers of propylene and other monomers (propylene copolymers). Propylene copolymers include propylene / ethylene copolymers, propylene / 1-butene copolymers, propylene / 1-pentene copolymers, propylene / 1-octene copolymers, etc.

[0037] It should be noted that the propylene units (component units derived from propylene) contained in the propylene copolymer need only constitute more than 50% (usually up to 99.999%) of all components, but may, for example, constitute 80 to 99.999% or 90 to 99.995% or even 99.0 to 99.990% of all components.

[0038] Furthermore, the polyolefin-based polymer may contain components derived from monomers other than olefins, as long as the subject matter of the present invention is not adversely affected. Monomers other than olefins include unsaturated carboxylic acids (acrylic acid, methacrylic acid, etc.), unsaturated carboxylic acid esters (methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, etc.), vinyl esters (vinyl acetate, vinyl propionate, fumaric acid, maleic anhydride, maleic acid monoester, etc.), and the like. Of the above, any one type may be used alone, or two or more types may be combined.It should be noted that the component units derived from monomers other than olefins contained in the polyolefin-based polymer, if present, preferably do not exceed 40% (normally at least 0.001%) of all component units. For example, they may constitute 0.001 to 25%, or 0.005 to 15%, or even 0.01 to 10% of all component units.

[0039] The density of the polyolefin-based resin is preferably 0.880 to 0.950 g / cm 3in terms of processability. The melt flow rate (MFR) is also preferably in the range of 1.0 to 10.0 g / 10 min from the perspective of mechanical strength and processability. This is because, if the resin has an appropriate viscosity during melt processing, the ammonium salt of carboxylic acid can be contained in the resin in the granulated state and covered by the resin, thus preventing the corrosion inhibitor from falling out of the resin molded product.

[0040] In addition, known resin additives such as antiblocking agents (AB agents), lubricants, antioxidants, antistatic agents, UV absorbers, and processability improving agents may be added to the resin layers 1, 2, as long as the effects of the present invention are not inhibited.

[0041] It should be noted that according to the present invention, a sufficient long-term anti-corrosive property can be realized without mixing an ionomer resin or a functional group-containing polyolefin resin into the resin layer 1 or resin layer 2 to keep the corrosion inhibitor in the resin layer.

[0042] Furthermore, the thickness of the resin layer 1 and the resin layer 2 is each independently 30 to 500 µm, preferably 30 to 200 µm.

[0043] Although the reason is unclear and the specific results vary depending on the type of metal to be protected from corrosion, the resin molded product, while achieving a certain degree of long-term anti-corrosive property in the molded product consisting only of a resin layer 1 containing only an ammonium salt of aromatic monocarboxylic acid alone (however, this aspect is not according to the invention), can provide a molded product with better long-term anti-corrosive property if the resin layer simultaneously contains one or more kinds of substances selected from sodium salt or potassium salt of carboxylic acid, carboxylic acid, benzotriazole-based compound and tolyltriazole-based compound.

[0044] Furthermore, the long-term anti-corrosive property can be further improved when the resin layer 1 containing an ammonium salt of aromatic monocarboxylic acid is covered with the resin layer 2 containing one or more kinds of substances selected from metal salt of aliphatic carboxylic acid, metal salt of nitrous acid, carboxylic acid, benzotriazole-based compound and tolyltriazole-based compound.

[0045] Although a detailed mechanism has not yet been identified, it is believed that adjusting the particle sizes of the ammonium salt of aromatic monocarboxylic acid within a certain range enables the formation of convexities on the film surface, thus realizing a long-term anti-corrosive effect. (Base material layer)

[0046] The resin molded product proposed according to the present invention may further comprise a base material layer provided on the surface on the resin layer 1 side and / or the resin layer 2 side.

[0047] The base material layer is provided with the aim, among other things, of imparting strength and gas and water vapor barrier properties to the molded product proposed by the present invention, as well as to improve its feel and aesthetics. Any material that does not inhibit the anti-corrosive effect achieved by the resin layers 1, 2 can be used as the material constituting the base material layer, and preferably the material has excellent adhesion to the resins constituting the resin layer 1 and the resin layer 2. Therefore, any of the aforementioned resins that can be used for the resin layer 1 and the resin layer 2, any resin having excellent adhesion to the resin layer 1 and the resin layer 2, or even woven fabric, nonwoven fabric, or paper can be used as the material constituting the base material layer.

[0048] When a resin is used, each resin layer can contain various known additives. Furthermore, each resin layer can be porous or non-porous.

[0049] Regarding the method for forming such a resin-based base material layer, the base material layer may be formed simultaneously with the formation of the resin layer 1 and / or the resin layer 2, or a method may be used in which the base material layer is formed separately from the resin layer 1 or the resin layer 2 and then overlaid by a known means. (Manufacture and use of resin molded products with resin layer 1)

[0050] A resin molded product having the resin layer 1 can be formed by any known means such as extrusion, inflation, vacuum forming, or compression molding, and can have any desired shape, such as a film, a sheet-like article, a bag-like article, a laminated sheet-like article, a cylinder, or a box. It can be used with its surface positioned on the resin layer 1 side on the inside of the container or packaging film, or specifically on the side of the article to be stored or packaged, thus being protected from rust formation; conversely, when a resin layer 2 is provided, it can be used with its surface positioned on the resin layer 2 side on the inside of the container or packaging film, or specifically on the side of the article to be stored or packaged, thus being protected from corrosion.

[0051] It should be noted that according to the present invention, the average particle size of the ammonium salt of aromatic monocarboxylic acid is within a certain range. However, due to their nature, ammonium salts of aromatic monocarboxylic acids can be crushed, and their average particle size may decrease when added to and kneaded with resins, as well as during the molding step; therefore, care should be taken to ensure that the specific average particle size specified in the present invention is achieved after molding.

[0052] As long as an ammonium salt of aromatic monocarboxylic acid with this specific particle size is included, the amount of anti-corrosive gas produced can be controlled and thus the anti-corrosive effect can be kept stable over a long period of time.

[0053] In addition, the use of two resin layers helps to maintain high corrosion protection effect more stably over a long period of time without adding carboxylic acid modified polyolefin-based polymer, wax, nonionic surfactant, inorganic porous medium or other delayed release agent of corrosion inhibitors, because the moisture slowly penetrates from the surface into the resin layer 2 or 1 and thus anticorrosive gas also slowly generates.

[0054] The range of items that are not intended to corrode also includes a wide range of items such as cast iron, steel sheets and galvanized steel sheets. Examples

[0055] The present invention is explained in more detail with reference to the following examples and comparative examples.

[0056] It should be noted that the examples each represent only one embodiment of the present invention and that the present invention is not limited to these examples.

[0057] Each of the corrosion protection components shown in Table 1 was added to 100 parts by weight of a low-density polyethylene (Sumikasen F200, manufactured by Sumitomo Chemical, density = 0.924 / cm 3, MFR = 2.0 g / 10 min) was added, and the ingredients were manually stirred and mixed to prepare each molded compound. Using the obtained compounds, tubular films were produced by an inflation extrusion apparatus at a mold temperature of 150°C. For molding, a single-layer apparatus was used in Examples 9, 11, and Comparative Examples 1 to 18, while a double-layer apparatus was used in Examples 15 and Comparative Examples 19 to 23 to obtain two layers with an identical density. ⊚ Corrosion protection test A. [Anticorrosive test using anticorrosive film]Each test piece as shown in [C] below was suspended with a nylon cord in a frame of 100 mm length × 100 mm width × 150 mm height, and the frame was sealed with each prepared film.

[0058] This test setup was maintained for each period in each test environment as specified in [B] below, after which the state of surface corrosion formation was evaluated based on the evaluation method according to [D] below. B. [Test environments] 25°C, 70% relative humidity: 4 hours 50°C, 95% relative humidity: 4 hours Transition time between settings: 2 hours, for a total duration of 12 hours per cycle. Evaluations: Medium-term effect: 3 days (6 cycles) Long-term effect: 7, 14 days (14, 28 cycles) C. [Test pieces] Cast iron (JIS G 5501), size: Ø30 mm × 8 mm Steel sheet (JIS G 3141), size: 1.2 mm × 30 mm × 50 mm Galvanized steel sheet (JIS H 8610), size: 1.4 mm × 30 mm × 50 mm D. [Evaluation criteria for corrosion protection] ⊚: No corrosion or discoloration ◯: Spot corrosion or slight discoloration Δ: Corrosion or discoloration of less than 10% of the test piece per area. X: Corrosion or discoloration of 10% or more but less than 50% of the test piece per area. XX: Corrosion or discoloration of 50% or more of the test piece per area [Measurement condition of the average particle size of the ammonium salt of aromatic monocarboxylic acid]

[0059] Resin layer 1 was photographed with a LEICA DFC295 stereomicroscope and the measurement was performed based on the photographed data.

[0060] It should be noted that since particles having a particle size of 10 µm or less were not measured, the term "average particle size" as used in the present invention represents a value obtained by the following formula based on a number of 1000 particles whose long diameter exceeds 10 m. Average particle size = (total sum of long diameters of particles larger than 10 μm) / number of particles

[0061] Examples 1 to 8, 10, 12 to 14, 16, and 17 are reference examples. Examples 9, 11, and 15 represent examples according to the invention. Resin layer 1 Resin layer 2 thickness Average particle size of the ammonium salt Maximum particle size of the ammonium salt cast iron sheet steel Galvanized steel sheet 3 days 7 days 14 days 3 days 7 days 14 days 3 days 7 days 14 days Example 1 Ammonium benzoate (1 part) 100 µm 21 µm 45 µm ⊚ ◯ × ⊚ ⊚ ◯ ⊚ ◯ Δ Example 2 Ammonium benzoate (1 part) 100 µm 28 µm 420 µm ⊚ ◯ × ⊚ ⊚ ◯ ⊚ ◯ Δ Example 3 Ammonium benzoate (0.1 parts) 100 µm 28 µm 420 µm ⊚ × ×× ⊚ ◯ Δ ⊚ Δ X Example 4 Ammonium benzoate (6 parts) 100 µm 28 µm 420 µm ⊚ ⊚ Δ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ Example 5 Ammonium benzoate (1 part) 100 µm 200 µm 1500 µm ⊚ Δ × ⊚ ⊚ ◯ ⊚ ◯ Δ Example 6 Ammonium benzoate (1 part) 100 µm 400 µm 3000 µm ⊚ Δ × ⊚ ⊚ ◯ ⊚ ◯ Δ Example 7 Ammonium benzoate (1 part) 60 µm 28 µm 420 µm ⊚ Δ × ⊚ ⊚ ⊚ ⊚ ◯ Δ Example 8 Ammonium benzoate (1 part) 200 µm 28 µm 420 µm ⊚ ⊚ Δ ⊚ ⊚ ⊚ ⊚ ⊚ Δ Example 9 Ammonium benzoate (1 part) + sodium sebacate (1 part) 100 µm 28 µm 420 µm ⊚ ⊚ Δ ⊚ ⊚ ⊚ ⊚ ⊚ Δ Example 10 Ammonium benzoate (1 part) + benzoic acid (1 part) 100 µm 28 µm 420 µm ⊚ ⊚ × ⊚ ⊚ ⊚ ⊚ ◯ Δ Example 11 Ammonium benzoate (1 part) + sodium sebacate (1 part) + benzotriazole (1 part) 100 µm 28 µm 420 µm ⊚ ⊚ Δ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Example 12 Ammonium benzoate (1 part) Sodium sebacate (1 part) 100 µm 28 µm 420 µm ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ Example 13 Ammonium benzoate (1 part) Sodium sebacate (0.2 parts) 100 µm 28 µm 420 µm ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ Example 14 Ammonium benzoate (0.1 parts) Sodium sebacate (1 part) 100 µm 28 µm 420 µm ⊚ ◯ Δ ⊚ ⊚ ◯ ⊚ ◯ ◯ Example 15 Ammonium benzoate (1 part)Sodium p-tert-butyl benzoate (1 part) Sodium caprylate (1 part) 100 µm 28 µm 420 µm ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ Example 16 Ammonium adipate (1 part) Sodium sebacate (1 part)Sodium nitrite (1 part) 100 µm 28 µm 420 µm ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ Example 17 Ammonium adipate (1 part)Benzotriazole (1 part) Sodium sebacate (1 part) Benzoic acid (1 part) 100 µm 28 µm 420 µm ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Comparison example 1 Ammonium benzoate (1 part) 100 µm 13 µm 20 µm ◯ × ×× ⊚ ◯ Δ ⊚ Δ × Comparison example 2 Ammonium benzoate (0.1 parts) 100 µm 13 µm 20 µm Δ ×× ×× ⊚ Δ × ⊚ × × Comparison example 3 Ammonium benzoate (6 parts) 100 µm 13 µm 20 µm ⊚ Δ × ⊚ ⊚ ◯ ⊚ ⊚ Δ Comparison example 4 Ammonium benzoate (1 part) 60 µm 13 µm 20 µm Δ × ×× ⊚ ◯ Δ ⊚ Δ × Comparison example 5 Ammonium benzoate (1 part) 200 µm 13 µm 20 µm ⊚ Δ × ⊚ ⊚ ◯ ⊚ ◯ Δ Comparison example 6 Ammonium benzoate (1 part) + sodium sebacate (1 part) 100 µm 13 µm 20 µm ⊚ ◯ × ⊚ ⊚ ◯ ⊚ ◯ Δ Comparison example 7 Sodium sebacate (1 part) 100 µm - - ×× ×× ×× × ×× ×× ◯ × × Comparison example 8 Benzotrialzole (1 part) 100 µm - - ×× ×× ×× × ×× ×× ⊚ ⊚ ⊚ EEEComparison Example 9 No encores 100 µm - - ×× ×× ×× × ×× ×× ◯ × ×

[0062] Examples 9 and 11 are examples of molded products consisting only of the resin layer 1, while Example 15 is an example of molded products consisting of the resin layer 1 (50 µm thickness) and the resin layer 2 (50 µm thickness) overlapping each other with a total thickness of 100 µm.

[0063] According to the results of Examples 9, 11 and 15, in which the average particle size of the ammonium salt of aromatic monocarboxylic acid was 20 µm or more, sufficient anti-corrosive property was realized for all cast iron, steel sheets and galvanized steel sheets in the medium term (3 days).

Claims

[1] A resin molded product having a polyolefin-based polymer resin layer 1 containing an ammonium salt of an aromatic monocarboxylic acid as specified below having an average particle size of 20 μm or more and a sodium salt or potassium salt of a carboxylic acid, wherein one or more kinds of the ammonium salt selected from ammonium salts of benzoic acid, aminobenzoic acid, salicylic acid, p-tert-butylbenzoic acid, o-sulfobenzoic acid, 1-naphthoic acid and 2-naphthoic acid may be contained. [2] The resin molded product according to claim 1, wherein the resin layer 1 contains one or more kinds of substances selected from carboxylic acid, benzotriazole compound and tolyltriazole compound. [3] The resin molded product according to claim 1 or 2, further covered with a base material layer. [4] The resin molded product according to claim 3, wherein the base material layer contains one or more kinds of substances selected from metal salt of nitrous acid, carboxylic acid, benzotriazole compound, tolyltriazole compound and metal salt of carboxylic acid. [5] A resin molded product according to any one of claims 1 to 4, which is a sheet-like article or a bag-like article.