Resin composition and hot melt adhesive composition

Abstract

The purpose of the present invention is to provide a resin composition having excellent water vapor barrier properties while maintaining the fluidity, adhesiveness, and thermal shock resistance of a resin that is excellent in low-pressure molding. A resin composition containing a polyolefin resin (A), an acid-modified polyolefin resin (B), a styrene-isobutylene-styrene block copolymer (C), an adhesion imparting agent (D), and a filler (E), when the total of the polyolefin resin (A), the acid-modified polyolefin resin (B), the styrene-isobutylene-styrene block copolymer (C), and the adhesion-imparting agent (D) is 100 parts by mass, the content of the styrene-isobutylene-styrene block copolymer (C) is 8-32 parts by mass, the content of the adhesion-imparting agent (D) is 8-27 parts by mass, and the content of the plate-shaped filler (E) is 1-13 parts by mass.

Description

Technical Field

[0001] The present invention relates to a resin composition, and more particularly to a resin composition and a hot-melt adhesive composition having excellent fluidity, water vapor barrier properties, adhesion, and thermal shock resistance. Background Art

[0002] Two-component curing epoxy resins and silicone resins are commonly used as insulating resins for sealing electrical and electronic components used in automobiles, electrical products, and the like. However, due to the long process times and the potential for damage to electrical and electronic components caused by shrinkage stress during curing, the use of low-pressure molding using thermoplastic resins for sealing electrical and electronic components has become common in recent years.

[0003] Polyester resins are suitable materials for sealing resins for electrical and electronic components from the perspectives of electrical insulation, water resistance, durability, and melt viscosity. However, during low-temperature, low-pressure molding, which is intended to reduce damage to electrical and electronic components, the adhesion between the electrical and electronic components and the sealing resin is often insufficient, and the intended electrical insulation and water resistance cannot be fully achieved. Therefore, to improve adhesion, active research and attempts have been made to incorporate adhesion-imparting agents containing functional groups (e.g., Patent Document 1). Prior art literature Patent Literature

[0004] Patent Document 1: Japanese Patent Application Laid-Open No. 2004-210893 Summary of the Invention Problems to be solved by the invention

[0005] In recent years, electrical and electronic components have been required to have high water vapor barrier properties in addition to the aforementioned required physical properties. However, when using thermoplastic resins mixed with tackifiers, as described in Patent Document 1, while adhesion is improved, there is a problem in that water vapor barrier properties cannot be ensured. Prior art has not yet proposed a sealing resin composition that can maintain the fluidity, adhesion, and thermal shock resistance of a resin that excels in low-pressure molding while also exhibiting water vapor barrier properties.

[0006] The present invention is based on the problems of the related prior art and aims to provide a resin composition having excellent water vapor barrier properties while maintaining the fluidity, adhesion, and thermal shock resistance of a resin excellent for low-pressure molding. Technical means to solve the problem

[0007] The present inventors have conducted intensive research and have found that the above-mentioned problems can be solved by the following means, thereby achieving the present invention. (1) A resin composition comprising a polyolefin resin (A), an acid-modified polyolefin resin (B), a styrene-isobutylene-styrene block copolymer (C), an adhesion-imparting agent (D) and a filler (E); wherein, based on 100 parts by mass of the total of the polyolefin resin (A), the acid-modified polyolefin resin (B), the styrene-isobutylene-styrene block copolymer (C) and the adhesion-imparting agent (D), the content of the styrene-isobutylene-styrene block copolymer (C) is 8 to 32 parts by mass, the content of the adhesion-imparting agent (D) is 8 to 27 parts by mass, and the content of the filler (E) is 1 to 13 parts by mass, wherein the filler (E) is in a plate-like shape. (2) The resin composition according to (1), wherein the polyolefin resin (A) contains a polypropylene resin and further contains at least one of an ethylene-α-olefin copolymer and a propylene-α-olefin copolymer. (3) The resin composition according to (1) or (2), wherein the acid-modified polyolefin resin (B) has a melting point of 100° C. or higher. (4) The resin composition according to any one of (1) to (3), wherein the styrene content of the styrene-isobutylene-styrene block copolymer (C) is 10 to 30% by weight. (5) The resin composition according to any one of (1) to (4), wherein the adhesion-imparting agent (D) has a hydroxyl value of 1 to 100 mgKOH / g. (6) The resin composition according to any one of (1) to (5), wherein the content of the polyolefin resin (A) is 38 to 70 parts by mass, and the content of the acid-modified polyolefin resin (B) is 1 to 22 parts by mass, based on 100 parts by mass of the total of the polyolefin resin (A), the acid-modified polyolefin resin (B), the styrene-isobutylene-styrene block copolymer (C) and the adhesion-imparting agent (D). (7) A hot melt adhesive composition comprising the resin composition according to any one of (1) to (6). Effects of the Invention

[0008] The resin composition of the present invention exhibits excellent low-pressure molding resin fluidity, adhesion, and thermal shock resistance, and further exhibits excellent water vapor barrier properties. Therefore, by using it as a sealing material for products requiring high water resistance, products that meet water vapor barrier requirements can be produced. In particular, the resin composition of the present invention can be used as a hot-melt adhesive and is particularly suitable for sealing electrical and electronic components. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] [ Figure 1 ] Figure 1 A schematic diagram showing a chart obtained by measurement using a differential scanning calorimeter. DETAILED DESCRIPTION

[0010] The present invention is described in detail below.

[0011] <Polyolefin resin (A)> The resin composition of the present invention contains a polyolefin resin (A). By containing a polyolefin resin (A), it is possible to impart good water vapor barrier properties to the resin composition. The polyolefin resin (A) used in the present invention is not particularly limited, but from the viewpoint of water vapor barrier properties, it is preferably a polypropylene resin. In addition, from the viewpoint of adhesion to metals and films, it is preferably an ethylene-α-olefin copolymer or a propylene-α-olefin copolymer. In order to achieve both water vapor barrier properties and adhesion properties, a polypropylene resin can also be used in combination with an ethylene-α-olefin copolymer or a propylene-α-olefin copolymer. The polypropylene resin herein refers to a so-called homopolypropylene (homopolypropylene) mainly composed of propylene units, and does not contain copolymer components such as α-olefins other than propylene, or even if it contains them, it is a very small amount of about 1 mol% at most. In addition, the polyolefin resin (A) does not belong to the acid-modified polyolefin resin (B) described later, but refers to a polyolefin resin that is not acid-modified.

[0012] When a polypropylene resin is used in combination with an ethylene-α-olefin copolymer and / or a propylene-α-olefin copolymer (hereinafter collectively referred to as an olefin copolymer) as the polyolefin resin (A), the preferred mixing ratio of the polypropylene resin / olefin copolymer is 20 / 80 to 80 / 20 by mass, more preferably 30 / 70 to 70 / 30, and even more preferably 40 / 60 to 60 / 40. By setting the ratio within this range, particularly high water vapor barrier properties and adhesiveness can be achieved.

[0013] The polyolefin resin (A) used in the present invention preferably has a melt flow rate (hereinafter referred to as MFR) measured by JIS K 7210-1:2014 (test temperature 190°C, nominal load 2.16 kg) of 10 to 70 g / 10 minutes. By setting it to be above the lower limit, the fluidity of the resin can be appropriately maintained, and the moldability is good. In addition, by setting it to be below the above upper limit, the resin composition can be prevented from being extremely softened due to a decrease in viscosity, and the mechanical properties are good. When the polyolefin resin (A) contains a plurality of polyolefin resins, each polyolefin resin is preferably within the above range.

[0014] When the resin composition of the present invention is used as a hot melt adhesive, it is required to melt rapidly at 210-240°C in order to minimize thermal degradation of the resin during molding. Therefore, the upper limit of the melting point of the polyolefin resin (A) is preferably 210°C. It is preferably 200°C or less, more preferably 190°C or less. The lower limit is preferably 90°C or more, more preferably 100°C or more, further preferably 110°C or more, and particularly preferably 120°C or more. It only needs to be 5-10°C higher than the heat-resistant temperature required for the application. When the polyolefin resin (A) contains multiple polyolefin resins, each polyolefin resin is preferably within the above range.

[0015] When the total amount of polyolefin resin (A), acid-modified polyolefin resin (B), styrene-isobutylene-styrene block copolymer (C) and adhesion imparting agent (D) is 100 parts by mass, the content of polyolefin resin (A) in the resin composition of the present invention is preferably 38 parts by mass or more, more preferably 40 parts by mass or more, further preferably 42 parts by mass or more, and particularly preferably 48 parts by mass or more. In addition, it is also preferably 70 parts by mass or less, more preferably 68 parts by mass or less, and further preferably 63 parts by mass or less. When the content ratio of polyolefin resin (A) is above the above lower limit, it is possible to impart particularly good water vapor barrier properties to the resin composition. In addition, if it is below the above upper limit, the heat shock resistance of the resin composition is good.

[0016] <Acid-modified polyolefin resin (B)> The resin composition of the present invention contains an acid-modified polyolefin resin (B). By containing the acid-modified polyolefin resin (B), good dispersibility can be imparted to the polyolefin resin (A), styrene-isobutylene-styrene block copolymer (C), adhesion-imparting agent (D), and filler (E), thereby imparting appropriate adhesion, heat shock resistance, and water vapor barrier properties to the resin composition. The acid-modified polyolefin resin (B) is not particularly limited, as long as it is a resin having a polyolefin block and a carboxylic acid block. Examples thereof include ethylene-unsaturated carboxylic acid copolymers such as ethylene-vinyl acetate-maleic anhydride terpolymer and ethylene-ethyl acrylate-maleic anhydride terpolymer, maleic anhydride-grafted modified polypropylene, maleic anhydride-grafted modified propylene-α-olefin copolymer, and unsaturated carboxylic acid graft-modified polyolefin resins. Among them, unsaturated carboxylic acid graft-modified polyolefin resins are preferred, and modified polyolefin resins in which the unsaturated carboxylic acid used for graft modification is maleic anhydride are more preferred.

[0017] The melting point of the acid-modified polyolefin resin (B) used in the present invention is preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher. Furthermore, it is preferably 160°C or lower, and more preferably 150°C or lower. When the melting point of the acid-modified polyolefin resin (B) is at least the lower limit, the heat resistance of the resin composition is excellent. When it is at most the upper limit, the flowability of the resin composition during molding is excellent.

[0018] When the total amount of polyolefin resin (A), acid-modified polyolefin resin (B), styrene-isobutylene-styrene block copolymer (C) and adhesion imparting agent (D) is 100 parts by mass, the content of the acid-modified polyolefin resin (B) in the resin composition of the present invention is preferably more than 1 part by mass, more preferably more than 3 parts by mass, and further preferably more than 5 parts by mass. It is also preferably less than 22 parts by mass, more preferably less than 20 parts by mass, further preferably less than 15 parts by mass, and particularly preferably less than 10 parts by mass. If the proportion of the acid-modified polyolefin resin (B) is more than the above-mentioned lower limit, the dispersibility with the polyolefin resin (A), styrene-isobutylene-styrene block copolymer (C), adhesion imparting agent (D) and filler (E) is good. In addition, if the proportion of the acid-modified polyolefin resin (B) is less than the above-mentioned upper limit, the mechanical properties are good.

[0019] <Styrene-isobutylene-styrene block copolymer (C)> The resin composition of the present invention contains a styrene-isobutylene-styrene block copolymer (C). By containing a styrene-isobutylene-styrene block copolymer (C), the resin composition can be given appropriate thermal shock resistance. The styrene-isobutylene-styrene block copolymer (C) used in the present invention is not particularly limited, but from the viewpoint of water vapor barrier properties and thermal shock resistance, a triblock structure is preferably used.

[0020] The styrene content of the styrene-isobutylene-styrene block copolymer (C) used in the present invention is preferably 10% by weight or more, more preferably 13% by weight or more, and further preferably 15% by weight or more. It is also preferably 30% by weight or less, more preferably 25% by weight or less, and further preferably 20% by weight or less. If the styrene content of the styrene-isobutylene-styrene block copolymer (C) is above the above lower limit, then the heat resistance is good. In addition, if the styrene content of the styrene-isobutylene-styrene block copolymer (C) is below the above upper limit, then the flexibility increases and the heat shock resistance is good.

[0021] When the total amount of polyolefin resin (A), acid-modified polyolefin resin (B), styrene-isobutylene-styrene block copolymer (C) and adhesion imparting agent (D) is 100 parts by mass, the content of styrene-isobutylene-styrene block copolymer (C) in the resin composition of the present invention needs to be 8 parts by mass or more. It is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 18 parts by mass or more. In addition, it is also necessary to be 32 parts by mass or less. It is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, further preferably 25 parts by mass or less, and particularly preferably 22 parts by mass or less. If the proportion of styrene-isobutylene-styrene block copolymer (C) is above the above lower limit, then the heat shock resistance is good. In addition, if the proportion of styrene-isobutylene-styrene block copolymer (C) is below the above upper limit, then the fluidity of the resin is high and the formability is good.

[0022] <Adhesive (D)> The resin composition of the present invention contains an adhesion imparting agent (D) (adhesion promoter). By containing the adhesion imparting agent (D), when the resin composition is used as a sealant, in addition to being able to impart good adhesion, the fluidity of the resin composition can be appropriately improved. The adhesion imparting agent (D) used in the present invention is not particularly limited, and phenolic compounds, xylene-modified phenolic resins, terpene-modified phenolic resins, hydrogenated terpene-modified phenolic resins after hydrogenation of terpene-modified phenolic resins, etc. can be used. In particular, from the viewpoint of compatibility with the polyolefin resin (A), xylene-modified phenolic resins and terpene-modified phenolic resins are preferred.

[0023] The adhesion-imparting agent (D) used in the present invention preferably has a hydroxyl group. By having a hydroxyl group, the adhesion-imparting agent (D) can enhance wettability to the substrate, improve adhesion to the substrate, and improve insulation properties. The hydroxyl value of the adhesion-imparting agent (D) is preferably 1 mgKOH / g or more, more preferably 30 mgKOH / g or more, and even more preferably 50 mgKOH / g or more. It is also preferably 100 mgKOH / g or less, more preferably 90 mgKOH / g or less, even more preferably 80 mgKOH / g or less, and particularly preferably 70 mgKOH / g or less. If the hydroxyl value is below the above upper limit, it is possible to maintain appropriate moisture permeability while improving adhesion.

[0024] The hydroxyl value can be measured by, for example, the potentiometric titration method specified in JIS K 0070:1992.

[0025] When the total of polyolefin resin (A), acid-modified polyolefin resin (B), styrene-isobutylene-styrene block copolymer (C) and adhesion imparting agent (D) is 100 mass parts, the content of the adhesion imparting agent (D) in the resin combination of the present invention needs to be more than 8 mass parts. It is preferably more than 10 mass parts, more preferably more than 13 mass parts, and more preferably more than 15 mass parts. In addition, it is also necessary to be less than 27 mass parts, preferably less than 25 mass parts, more preferably less than 22 mass parts, and more preferably less than 20 mass parts. If the content of adhesion imparting agent (D) is within the above range, it is possible to show particularly good adhesion. In addition, the pliability decline of the resin combination, the adhesion decline caused by embrittlement, etc. can also be suppressed.

[0026] <Filler (E)> The resin composition of the present invention contains a filler (E). By containing a filler (E), the resin composition can be given good water vapor barrier properties. The filler (E) used in the present invention is not particularly limited, and glass microspheres, calcium carbonate, kaolin, talc, glass fiber, carbon fiber, clay, etc. can be used. The filler (E) used in the present invention is plate-shaped. By setting the filler (E) to a plate shape, the water vapor barrier properties can be particularly improved. Here, plate-shaped refers to a plate-like shape with an extremely small height compared to the width and depth of the filler. The aspect ratio of the filler (E), that is, the ratio of the minor diameter to the major diameter of the filler (E) (major diameter / minor diameter) is preferably 3 to 500. The aspect ratio of the filler (E) can be 5 or more, 10 or more, 20 or more, 50 or more, 100 or more, and can also be 450 or less, 400 or less, 350 or less, 300 or less, or 200 or less. The aspect ratio of the filler (E) can be obtained by automatic area calculation of an image obtained by observing the filler (E) with an electron microscope. When the aspect ratio of the filler (E) is too low, the water vapor barrier properties may be reduced. When the aspect ratio is too high, the dispersibility may be deteriorated, and the mechanical properties may be reduced.

[0027] When the total of polyolefin resin (A), acid-modified polyolefin resin (B), styrene-isobutylene-styrene block copolymer (C) and adhesion imparting agent (D) is 100 parts by mass, the content of the filler (E) in the resin composition of the present invention needs to be more than 1 part by mass, preferably more than 2 parts by mass, more preferably more than 4 parts by mass. If the content of filler (E) is above the above lower limit, the water vapor barrier is good. In addition, there is a situation where the mechanical properties of the resin composition are good and the shear bonding strength is improved. In addition, the content of filler (E) needs to be less than 13 parts by mass, preferably less than 10 parts by mass, more preferably less than 8 parts by mass. If the content of filler (E) is below the above upper limit, the adhesion is good.

[0028] The particle size (D50) of the filler (D) in the resin composition of the present invention may be, for example, 1 to 50 μm. The particle size (D50) can be measured, for example, by laser diffraction or dynamic light scattering.

[0029] <Resin Composition> The resin composition of the present invention contains at least the aforementioned polyolefin resin (A), acid-modified polyolefin resin (B), styrene-isobutylene-styrene block copolymer (C), tackifier (D), and filler (E), and may further contain various additives such as antioxidants as needed.

[0030] The melt viscosity of the resin composition of the present invention at 240°C is preferably 5 to 1500 dPa·s. The melt viscosity of the resin composition can be achieved by appropriately adjusting the types and mixing ratios of the polyolefin resin (A), the acid-modified polyolefin resin (B), the styrene-isobutylene-styrene block copolymer (C), the adhesion imparting agent (D) and the filler (E). In addition, the melt viscosity at 240°C here is a value measured as follows. That is, the resin composition is dried to a moisture content of less than 0.1%, and then the resin composition stably heated to 240°C is subjected to a capillary rheometer (model CFT-500C) manufactured by Shimadzu Corporation at a flow rate of 98 N / cm 2 The viscosity is measured when the resin composition is passed through a mold with a 1.0 mm pore size and a thickness of 10 mm at a pressure of . By using a resin composition with a melt viscosity of 1500 dPa·s or less, preferably 1000 dPa·s or less, it is possible to obtain a product with excellent electrical insulation at a relatively low injection pressure of 0.1 to 20 MPa without compromising the characteristics. In addition, from the viewpoint of the resin composition injection operation, the melt viscosity at 230°C is preferably lower. Considering the adhesion and cohesion of the resin composition, the lower limit is preferably 5 dPa·s or more, more preferably 10 dPa·s or more, more preferably 30 dPa·s or more, and most preferably 50 dPa·s or more.

[0031] The resin composition of the present invention may further contain an antioxidant. The antioxidant used in the present invention is not particularly limited as long as it can prevent the oxidation of the polyolefin resin (A), and hindered phenol antioxidants, phosphorus antioxidants, thioether antioxidants, etc. can be used. For example, hindered phenols include: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tris(4-hydroxy-2-methyl-5-tert-butylphenyl)butane, 1,1-bis(3-tert-butyl-6-methyl-4-hydroxyphenyl)butane, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenylpropionic acid, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl-phenylpropionic acid, 3,9 -bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)benzene; as phosphorus-based, 3,9-bis(p-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di(octadecyloxy)-2,4,8,10-tetraoxa-3 ,9-diphosphaspiro[5.5]undecane, tris(monononylphenyl)phosphite, triphenoxyphosphine, isodecylphosphite, isodecylphenylphosphite, diphenyl 2-ethylhexylphosphite, dinonylphenyl di(nonylphenyl)phosphate, 1,1,3-tris(2-methyl-4-di(tridecyl)phosphite-5-tert-butylphenyl)butane, tris(2,4-di-tert-butylphenyl)phosphite, pentaerythritol di(2,4-di-tert-butylphenylphosphite), 2,2'-methylenebis(4,6-di-tert-butylphenyl) 2-Ethylhexyl phosphite, di(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite; examples of thioethers include: 4,4'-thiobis[2-tert-butyl-5-methylphenol]bis[3-(dodecylthio)propionate], thiobis[2-(1,1-dimethylethyl)-5-methyl-4,1-phenylene]bis[3-(tetradecylthio)-propionate], pentaerythritol tetrakis(3-n-dodecylthiopropionate), and bis(tridecyl)thiodipropionate. These can be used alone or in combination.

[0032] The content of the antioxidant is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.3 parts by mass or more, relative to 100 parts by mass of the total of the polyolefin resin (A), the acid-modified polyolefin resin (B), the styrene-isobutylene-styrene block copolymer (C), and the adhesion-imparting agent (D). When the content is too low, there is a case where the long-term durability at high temperatures is negatively affected. In addition, there is also preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less. When the content is too high, there is a case where it has a negative impact on adhesion, etc.

[0033] In the resin composition of the present invention, other resins such as polyamide, polycarbonate, acrylic acid, ethylene-vinyl acetate, etc., curing agents such as isocyanate compounds, melamine, pigments such as carbon black and titanium oxide, flame retardants such as antimony trioxide, and brominated polystyrene, which are not included in any of the polyolefin resin (A), acid-modified polyolefin resin (B), styrene-isobutylene-styrene block copolymer (C), adhesion-imparting agent (D), and filler (E), can be mixed within a range that does not impair the effects of the present invention. By mixing these components, there are cases where adhesion, flexibility, durability, etc. are improved. In this case, the polyolefin resin (A) preferably contains 30 to 70% by weight, more preferably 40 to 60% by weight, relative to the entire resin composition of the present invention. When the content of the polyolefin resin (A) is too low, there is a tendency for the excellent water vapor barrier and durability of the polyolefin resin (A) itself to decrease; when it is too high, there is a tendency for flexibility and adhesion to decrease.

[0034] Furthermore, when the resin composition of the present invention requires weather resistance, it is preferable to add a light stabilizer. Examples of the light stabilizer include benzotriazole-based light stabilizers, benzophenone-based light stabilizers, hindered amine-based light stabilizers, nickel-based light stabilizers, and benzoate-based light stabilizers. Examples of the benzotriazole-based light stabilizer include 2-(3,5-di-tert-amyl-2'hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, and 2-[2-hydroxy-3,5-bis(1,1-dimethylbenzyl)]-2H-benzotriazole. Examples of the benzophenone-based light stabilizer include 2-hydroxy-4-(octyloxy)benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, 2-hydroxy-4-n-dodecyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone. Examples of hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-

[0014] Examples of nickel-based light stabilizers include [2,2'-thiobis(4-tert-octylphenol)]-2-ethylhexylamine-nickel (II), nickel dibutyldithiocarbamate, and [2',2'-thiobis(4-tert-octylphenol)]-n-butylamine-nickel. Examples of benzoate-based light stabilizers include 2,4-di-tert-butylphenyl-3,5'-di-tert-butyl-4'-hydroxybenzoate. These light stabilizers can be used alone or in combination. The amount added is preferably 0.1% to 5% by mass relative to the total resin composition. A content below 0.1% by mass may result in a lack of weather resistance. A content exceeding 5% by mass may negatively impact adhesion and other properties.

[0035] <Hot Melt Adhesive Composition> The resin composition of the present invention can be used as a hot melt adhesive composition. As a hot melt adhesive composition, it can be suitably used as a sealant for electrical and electronic components, for example. As a specific example of a method of use, the resin composition of the present invention can be injected into a mold provided with a product to be waterproofed, and the product can be sealed to obtain a molded body. More specifically, when using a screw-type hot melt molding applicator, the resin composition can be heated and melted at around 180 to 250°C, injected into the mold through an injection nozzle, and then, after a certain cooling time, the molded product can be removed from the mold to obtain a molded product.

[0036] The type of applicator for hot melt molding is not particularly limited, but examples thereof include the vertical extruder IMC-18F9 manufactured by Imoto Manufacturing Co., Ltd. and the hybrid small vertical injection molding machine STX20 and THX5S1VN manufactured by Nissei Plastic Industry Co., Ltd. Example

[0037] In order to further illustrate the present invention, the following examples and comparative examples are given, but the present invention is not limited to these examples. In addition, each measurement value described in the examples and comparative examples was measured by the following method.

[0038] <Determination of Melting Point> Using a differential scanning calorimeter "DSC220" manufactured by Seiko Instruments, 5 mg of the test sample (polyolefin resin (A) or acid-modified polyolefin resin (B)) was placed in an aluminum pan, covered and sealed, and first heated to 230°C at a heating rate of 20°C / min to melt. Next, using liquid nitrogen, it was cooled to -130°C at a rate of 20°C / min, held for 5 minutes, and then heated from -130°C to 230°C at a heating rate of 20°C / min for measurement. The obtained curve is shown in Figure 2. Figure 1 The minimum point of the endothermic peak shown (marked with "X" in the figure) was taken as the melting point (Tm).

[0039] <Hydroxy Value> The hydroxyl value of the tackifier (D) can be measured by the potentiometric titration method specified in JIS K 0070:1992.

[0040] <Melt Viscosity> Using a capillary rheometer (CFT-500C model) manufactured by Shimadzu Corporation, a mixed raw material or resin composition dried to a moisture content of 0.1% or less was filled into the cylinder in the center of a heating body set at 240°C. After 1 minute of filling, a load was applied to the sample via a rod at a pressure of 98 N / cm 2The molten sample was extruded through a die (aperture: 1.0 mm, thickness: 10 mm) at the bottom of the barrel. The distance and time the rod descended were recorded to calculate the melt viscosity. Based on the melt viscosity, the melt properties (fluidity) were evaluated according to the following evaluation criteria. Evaluation Criteria 0: Melt viscosity at 240°C is 5 dPa·s or more and less than 1000 dPa·s △: Melt viscosity at 240°C is 1000 dPa·s or more and less than 1500 dPa·s ×: Melt viscosity at 240°C is 1500 dPa·s or higher

[0041] <Water vapor barrier properties> A film having a thickness of about 120 μm was produced from the resin composition by hot pressing using a hot press machine (SA-303 manufactured by Tester Sangyo Co., Ltd.). Hot pressing conditions were set at 200°C, a press pressure of 10 MPa, and a press time of 30 seconds. Test pieces conforming to JIS Z0208:1976 were cut from the hot-pressed film using a cutter. The film was then mounted on a jig specified in JIS Z0208:1976 and allowed to stand for a total of approximately 96 hours in an environment of 25°C and 90% relative humidity (RH). Samples were removed 24 hours, 48 ​​hours, 72 hours, and 96 hours after the start of the test and their weights were measured. The moisture permeability (water vapor barrier property) was calculated based on the weight of water absorbed by calcium chloride every 24 hours between (1) 24 and 48 hours, (2) 48 and 72 hours, and (3) 72 and 96 hours. The average of the three moisture permeability values ​​was used as the moisture permeability. The moisture permeability was calculated using the following formula. The moisture permeability area refers to the area of ​​the film made from the resin composition. Moisture permeability (g / (m 2 24h))=(240×m) / (t×s) m: The total amount of mass added during the last two weighing intervals of the test (mg) t: The time between the last two weighings of the test = 24h s: moisture permeability area (cm 2 ) Evaluation criteria: ◎: Moisture permeability less than 0.5 (g / (m 2 24h)) ○: Moisture permeability is 0.5 (g / (m 2 ·24h)) and less than 1.0(g / (m 2 24h)) △: Moisture permeability is 1.0(g / (m 2·24h)) and less than 1.5(g / (m 2 24h)) ×: Moisture permeability 1.5 (g / (m 2 ·24h)) or more

[0042] <Adhesion Test (T Peel Adhesion Strength)> Method for preparing T peel adhesion test piece The substrate (aluminum substrate: A5052 (thickness: 0.1mm)) was cut into a size of 40mm×25mm, and the surface was wiped with acetone to remove oil. Next, a hot press machine (SA-303 manufactured by Tester Industry Co., Ltd.) was used to make a film with a thickness of about 200μm from the resin composition by hot pressing. The hot pressing conditions were set to a temperature of 200°C, a pressing pressure of 6MPa, and a pressing time of 10 seconds. The hot-pressed film was cut into a size of 20mm×25mm, two pieces were overlapped, and sandwiched between the pre-cut aluminum substrates. Heat sealing was performed using a heat sealing tester (TP-701-B manufactured by Tester Industry Co., Ltd.). The heat sealing conditions were set to a temperature of 220°C, a pressure of 0.4MPa, and a pressing time of 30 seconds to obtain a T peeling adhesion test piece in which a film composed of a resin composition was clamped by an aluminum substrate.

[0043] T peel adhesion strength test method Using a universal testing machine (AG-IS, manufactured by Shimadzu Corporation), the aluminum substrate was clamped with a clamp. T-peel testing was performed at 25°C or 90°C to peel the film layer composed of the resin composition from the T-peel test piece to measure the T-peel strength. The tensile speed was set to 300 mm / min. Evaluation criteria: ○: T-peel adhesive strength is 70N / 25mm or more △: T peel strength is 40N / 25mm or more and less than 70N / 25mm ×: T peel strength is less than 40N / 25mm

[0044] <Thermal shock resistance test> Method for preparing thermal shock resistance test samples A 30 mm long side of a substrate (aluminum substrate: A5052 (40 mm × 30 mm × 5 mm thickness)) was cut to 30 mm × 1 mm × 1 mm, and the cut portion was sandblasted to an Rz (surface roughness) of about 5 μm, and the surface was wiped with acetone to remove oil. Next, the substrate was placed in a specified mold, and an injection molding machine (a hybrid small vertical injection molding machine THX5S1VN manufactured by Nissei Plastic Industry Co., Ltd.) was used to injection mold the resin composition into the cut portion. The injection molding conditions were set to a temperature of 240°C, a mold temperature of 80°C, an injection speed of 30 mm / s, a holding pressure of 50 MPa, an injection time of 10 seconds, a holding pressure time of 20 seconds, and a pressing time of 10 seconds to obtain a heat shock resistance test sample in which the resin composition was bonded to the cut aluminum substrate portion.

[0045] Thermal shock resistance test method The thermal shock resistance test sample was tested using a thermal shock test tank (TSE-11 manufactured by ESPEC Corporation) at -45°C and 95°C (one cycle: -45°C for 9 minutes, 95°C for 10 minutes) for up to 2000 cycles. Evaluation criteria: ○: After 2000 cycles, no cracking of the resin composition or peeling from the aluminum substrate occurred ×: After 2000 cycles, the resin composition cracked and peeled off from the aluminum substrate.

[0046] <Examples 1 to 9, Comparative Examples 1 to 8> Polyolefin resin (A), acid-modified polyolefin resin (B), styrene-isobutylene-styrene block copolymer (C) (resin composition 17 is a styrene-ethylene-butylene-styrene block copolymer), tackifier (D), and filler (E) were melt-kneaded in the proportions listed in Table 1 using a twin-screw extruder at a die temperature of 160°C to 220°C to produce resin compositions 1 to 17. The resin compositions were evaluated for melt viscosity, water vapor barrier properties, T-peel adhesion strength, and thermal shock resistance using methods described separately. The evaluation results are shown in Table 1 below.

[0047] [Table 1]

[0048] The polyolefin resin, acid-modified polyolefin resin, styrene-isobutylene-styrene block copolymer, tackifier, and filler used in Table 1 are as follows. Polyolefin resin (A-1): J107G, manufactured by Prime Polymer Co., Ltd., homopolymer polypropylene resin, melting point: 165°C, density: 0.90 g / cm 3 Polyolefin resin (A-2): EUL731, manufactured by Sumitomo Chemical Co., Ltd., ethylene-α-olefin copolymer, melting point: 113-117°C, density: 0.90 g / cm 3 Polyolefin resin (A-3): TAFMERPN-20300, manufactured by Mitsui Chemicals, Inc., propylene-α-olefin copolymer, melting point: 160°C, density: 0.87 g / cm 3 Acid-modified polyolefin resin (B-1): PMA H1100P, manufactured by Toyobo Co., Ltd., maleic anhydride grafted modified polypropylene resin, melting point: 147°C, molecular weight Mw: 74000 Styrene-isobutylene-styrene block copolymer (C-1): SIBSTAR 062T, manufactured by Kaneka Co., Ltd., styrene-isobutylene-styrene block copolymer, styrene content: 23% by weight, MFR: 10 g / 10 min (230°C, 2.16 kg), density: 0.95 g / cm 3 Styrene-isobutylene-styrene block copolymer (C-2): SIBSTAR 102T, manufactured by Kaneka Co., Ltd., a styrene-isobutylene-styrene block copolymer, styrene content: 15 wt%, MFR: 0.6 g / 10 min (230°C, 2.16 kg), density: 0.94 g / cm 3 Adhesive (D-1): YS Polystar T160, manufactured by Yasuhara Chemical Co., Ltd., terpene-modified phenolic resin, hydroxyl value: 60 mgKOH / g Adhesive (D-2): YS Polystar G150, manufactured by Yasuhara Chemical Co., Ltd., terpene-modified phenolic resin, hydroxyl value: 140 mgKOH / g Filler (E-1): K-1, manufactured by Nippon Talc Co., Ltd., talc, plate-shaped, particle size (D50): 8.0 μm, aspect ratio: 3 to 10 Filler (E-2): I.44P, manufactured by Volclay Japan Co., Ltd., montmorillonite, plate-shaped, size: 14-18 μm, aspect ratio: 100-500 Filler (E-3): UBS-0005E, manufactured by UNITIKA Co., Ltd., glass microspheres, spherical, particle size: ~5 μm, aspect ratio: 1 Styrene-ethylene-butylene-styrene block copolymer (F-1): Toughtech H1043, manufactured by Asahi Kasei Corporation, styrene-ethylene-butylene-styrene block copolymer, styrene content: 67% by weight, MFR: 2.0 g / 10 min (230°C, 2.16 kg), density: 0.97 g / cm 3

[0049] As clearly shown in Table 1, the resin compositions of Examples 1 to 9 exhibit excellent results in terms of melt viscosity (fluidity), moisture permeability (water vapor barrier properties), T-peel adhesion strength (adhesion), and thermal shock resistance. On the other hand, in Comparative Example 1, the water vapor barrier properties were poor due to the absence of filler. In Comparative Example 2, the melt viscosity was high due to the high filler content, resulting in poor adhesion and thermal shock resistance. In Comparative Example 3, the water vapor barrier properties were poor due to the presence of spherical fillers. In Comparative Example 4, the amount of adhesion-imparting agent was low, resulting in increased melt viscosity and poor adhesion. In Comparative Example 5, the adhesion was reduced due to the excessive amount of adhesion-imparting agent. In Comparative Example 6, the thermal shock resistance was poor due to the absence of styrene-isobutylene-styrene block copolymer. In Comparative Example 7, the amount of styrene-isobutylene-styrene block copolymer was high, resulting in poor adhesion. In Comparative Example 8, since a styrene-ethylene-butylene-styrene block copolymer was used instead of a styrene-isobutylene-styrene block copolymer, the moisture permeability and the adhesiveness were inferior. Industrial applicability

[0050] The resin composition of the present invention has a low melt viscosity during product molding, excellent adhesion to aluminum substrates, and excellent water vapor barrier properties and thermal shock resistance, and is therefore useful as a hot melt adhesive composition for waterproofing applications.

Claims

1. A resin composition comprising a polyolefin resin (A), an acid-modified polyolefin resin (B), a styrene-isobutylene-styrene block copolymer (C), an adhesion-imparting agent (D), and a filler (E); wherein, based on 100 parts by mass of the total of the polyolefin resin (A), the acid-modified polyolefin resin (B), the styrene-isobutylene-styrene block copolymer (C), and the adhesion-imparting agent (D), the content of the styrene-isobutylene-styrene block copolymer (C) is 8 to 32 parts by mass, the content of the adhesion-imparting agent (D) is 8 to 27 parts by mass, and the content of the filler (E) is 1 to 13 parts by mass, wherein the filler (E) is in a plate-like shape. 2 . The resin composition according to claim 1 , wherein the polyolefin resin (A) comprises a polypropylene resin and further comprises at least one of an ethylene-α-olefin copolymer and a propylene-α-olefin copolymer. 3 . The resin composition according to claim 1 , wherein the acid-modified polyolefin resin (B) has a melting point of 100° C. or higher. 4 . The resin composition according to claim 1 , wherein the styrene content of the styrene-isobutylene-styrene block copolymer (C) is 10 to 30% by weight. The resin composition according to claim 1 , wherein the adhesion-imparting agent (D) has a hydroxyl value of 1 to 100 mgKOH / g.

6. The resin composition according to claim 1, wherein the content of the polyolefin resin (A) is 38 to 70 parts by mass, and the content of the acid-modified polyolefin resin (B) is 1 to 22 parts by mass, based on 100 parts by mass of the total of the polyolefin resin (A), the acid-modified polyolefin resin (B), the styrene-isobutylene-styrene block copolymer (C), and the adhesion-imparting agent (D). 7 . A hot melt adhesive composition comprising the resin composition according to claim 1 .

Images