Resin composition, connection structure for solar power generation module, and junction box for solar power generation module

Abstract

To provide a resin composition combining high oil resistance and fire retardancy.SOLUTION: (a) (a-1) a polyphenylene ether resin, or a mixed resin of (a-1) component and (a-2) a styrene resin, (b) a hydrogenated block copolymer, and (c) a phosphate ester compound and (d) a polyolefin resin, relative to a total mass 100 pts.mass of the (a) component and (b) component, (a): 60 to 90 pts.mass, (b): 10 to 40 pts.mass, (c): 8 to 25 pts.mass, (d): 1 to 10 pts.mass, and when component (a) is a mixed resin, relative to 100 pts.mass of the mixed resin, (a-1): 55 to 99.95 pts.mass, the melt flow rate of component (d) is 30 g / 10 minutes or more, and a phase containing the component (a) forms a continuous phase. A connection structure for a photovoltaic module or a junction box for the photovoltaic module containing a molded body of the resin composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition, a connection structure for a photovoltaic module, and a junction box for a photovoltaic module.

Background Art

[0002] Conventionally, polyphenylene ether-based resins have excellent electrical insulation properties, heat resistance, hydrolysis resistance, and flame retardancy, and are therefore widely used in electrical and electronic components used in secondary batteries or photovoltaic power generation, home appliances, OA equipment, etc.

[0003] On the other hand, polyphenylene ether-based resin compositions do not have sufficient oil resistance, and cracks or fractures may occur due to contact with rust preventives adhering to the molds of molding machines, lubricating oils for various application parts, etc., often causing problems.

[0004] Regarding such problems, for example, Patent Document 1 describes that in a resin composition composed of a polypropylene-based resin and a polyphenylene ether-based resin, an oil-resistant resin composition excellent in heat resistance and flame retardancy with a continuous phase being a polypropylene-based resin can be obtained.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, there was room for achieving both high oil resistance and flame retardancy.

[0007] Therefore, an object of the present invention is to provide a resin composition that achieves both high oil resistance and flame retardancy.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, in a resin composition containing (a) a polyphenylene ether resin or a mixed resin of a polyphenylene ether resin and a styrene resin, (b) a hydrogenated block copolymer, (c) a phosphate ester compound, and (d) a polyolefin resin having a predetermined melt flow rate, it has been found that by setting the content of each component within a specific range and forming a continuous phase with the phase containing the (a) component, the above problems can be advantageously solved, and the present invention has been completed.

[0009] That is, the present invention is as follows. First Aspect: (a) (a-1) a polyphenylene ether resin, or a mixed resin of (a-1) a polyphenylene ether resin and (a-2) a styrene resin, (b) a hydrogenated block copolymer, (c) a phosphate ester compound, (d) a polyolefin resin, comprising, with respect to a total of 100 parts by mass of the (a) component and the (b) component, the amount of the (a) component is 60 to 90 parts by mass, the amount of the (b) component is 10 to 40 parts by mass, the amount of the (c) component is 8 to 25 parts by mass, the amount of the (d) component is 1 to 10 parts by mass, when the (a) component is the mixed resin, the amount of the (a-1) polyphenylene ether resin is 55 to 99.95 parts by mass with respect to 100 parts by mass of the mixed resin, the melt flow rate of the (d) component is 30 g / 10 min or more, a resin composition in which the phase containing the (a) component forms a continuous phase. Second Aspect: The resin composition according to the first aspect, wherein the amount of the (c) component is 10 to 20 parts by mass with respect to a total of 100 parts by mass of the (a) component and the (b) component. Aspect 3: The resin composition according to the first or second aspect, wherein the amount of the component (d) is 2 to 8 parts by mass with respect to a total of 100 parts by mass of the component (a) and the component (b). Aspect 4: The resin composition according to any one of the first to third aspects, wherein the component (c) is a phosphate ester compound represented by the following general formula (I) or general formula (II). [Chemical formula] [Chemical formula] (In general formula (I), Q1, Q2, Q3, and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms, R11 and R12 represent a methyl group, and R13 and R14 each independently represent a hydrogen atom or a methyl group. In general formula (II), Q1, Q2, Q3, and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms, and R11 and R12 represent a methyl group. y is an integer of 1 or more, n1 and n2 each independently represent an integer of 0 to 2, and m1, m2, m3, and m4 each independently represent an integer of 0 to 3.) Aspect 5: A connection structure for a photovoltaic module, including a molded body of the resin composition according to any one of the first to fourth aspects. Aspect 6: A junction box for a photovoltaic module, including a molded body of the resin composition according to any one of the first to fourth aspects. [Advantages of the Invention]

[0010] According to the present invention, a resin composition having both high oil resistance and flame retardancy can be obtained. [Modes for Carrying Out the Invention]

[0011] Hereinafter, modes for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an exemplification for explaining the present invention and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of its gist.

[0012] In this embodiment, (a-1) polyphenylene ether resin, (a-2) styrene resin, (b) hydrogenated block copolymer, (c) phosphate ester compound, and (d) polyolefin resin may be referred to as component (a-1), component (a-2), component (b), component (c), and component (d), respectively. Further, in this embodiment, component (a-1) alone, or component (a-1) and component (a-2) together may be referred to as component (a).

[0013] In this embodiment, the number average molecular weight is a value measured using a gel permeation chromatography measuring device equipped with an ultraviolet spectroscopic detector and converted to standard polystyrene.

[0014] In this embodiment, the melt flow rate (hereinafter sometimes referred to as "MFR") refers to a value measured in accordance with JIS K7210. Unless otherwise specified in this specification, JIS K7210, and the JIS standards of each resin, the measurement load for MFR is 2.16 kg. For example, the measurement conditions for the MFR of polypropylene, polyethylene, ethylene-vinyl acetate copolymer, and polybutene are described in JIS K6921-2, JIS K6922-2, JIS K6924-2, and JIS K6925-2, respectively. Further, for example, MFR (230 °C, 2.16 kg) means the MFR measured under the conditions of a temperature of 230 °C and a load of 2.16 kg. It is desirable to select an appropriate temperature for measuring the melt flow rate according to the type of resin to be measured. For example, it is 230 °C for polypropylene and 190 °C for polyethylene. Further, when component (d) consists of a plurality of different polyolefin resins, the measurement temperature adopts the measurement temperature of the polyolefin resin that accounts for 50% or more of the total mass of the polyolefin resins.

[0015] · Resin composition The resin composition of this embodiment is (a) (a-1) polyphenylene ether resin, or a mixed resin of (a-1) polyphenylene ether resin and (a-2) styrene resin, and (b) hydrogenated block copolymer, and (c) a phosphate ester compound, and (d) a polyolefin resin, wherein the total amount of the components (a) and (b) is 100 parts by mass, the amount of the component (a) is 60 to 90 parts by mass, the amount of the component (b) is 10 to 40 parts by mass, the amount of the component (c) is 8 to 25 parts by mass, the amount of the component (d) is 1 to 10 parts by mass, when the component (a) is the mixed resin, the amount of the (a-1) polyphenylene ether resin is 55 to 99.95 parts by mass with respect to 100 parts by mass of the mixed resin, the melt flow rate of the component (d) is 30 g / 10 min or more, and the phase containing the component (a) forms a continuous phase, and it is a resin composition.

[0016] Component (a) The component (a) of the present embodiment is an (a-1) polyphenylene ether resin or a mixture of an (a-1) polyphenylene ether resin and an (a-2) styrene resin.

[0017] The component (a) may be only one type or a combination of two or more types.

[0018] · Component (a-1) As the component (a-1) contained in the resin composition of the present embodiment, any of a homopolymer composed of a structural unit of the following general formula (III) and a copolymer having a structural unit of the general formula (III) (hereinafter, may be simply referred to as "polyphenylene ether") can be used.

Chemical formula

[0019] Examples of the homopolymer of the polyphenylene ether-based resin include, but are not limited to, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), and the like.

[0020] Examples of the copolymer of the polyphenylene ether-based resin include, but are not limited to, copolymers of 2,6-dimethylphenol and other phenols (for example, copolymers with 2,3,6-trimethylphenol, copolymers with 2-methyl-6-butylphenol).

[0021] Among these, as the polyphenylene ether-based resin, from the viewpoints of the balance of mechanical properties and productivity, poly(2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or a mixture thereof is preferable.

[0022] Examples of the method for producing the polyphenylene ether-based resin used in this embodiment include, but are not limited to, the known production methods described in U.S. Patent Nos. 3306874, 3306875, 3257357, and 3257358, Japanese Patent Application Laid-Open No. 50-51197, Japanese Patent Publication No. 52-17880, Japanese Patent Application Laid-Open No. 63-152628, and the like.

[0023] The reduced viscosity of the polyphenylene ether resin preferably ranges from 0.30 to 0.65 dL / g from the viewpoints of molding fluidity and physical property balance. More preferably, it ranges from 0.40 to 0.60 dL / g, and still more preferably, it ranges from 0.45 to 0.55 dL / g. If the reduced viscosity is 0.30 dL / g or more, the impact resistance or oil resistance is excellent. Further, if the reduced viscosity is 0.65 dL / g or less, the molding fluidity is excellent. In the present embodiment, the reduced viscosity of the polyphenylene ether resin is a value measured with a Ubbelohde viscometer at 30 °C using a 0.5 g / dL chloroform solution.

[0024] In the present embodiment, a mixture of two or more polyphenylene ether resins having different reduced viscosities can also be preferably used.

[0025] Further, the (a-1) polyphenylene ether resin of the present embodiment may contain a modified polyphenylene ether in which all or part is modified. The modified polyphenylene ether referred to herein means a polyphenylene ether modified with a modified compound having at least one carbon-carbon double bond or triple bond in the molecule and at least one group selected from the group consisting of a carboxylic acid group, an acid anhydride group, an amino group, a hydroxy group, and a glycidyl group (hereinafter, may be simply referred to as "modified compound"). Only one kind of modified compound may be used, or two or more kinds may be used in combination.

[0026] The method for producing the modified polyphenylene ether is not limited to the following, but for example, in the presence or absence of a radical initiator, (1) a method of reacting with a modified compound at a temperature in the range of 100 °C or higher and lower than the glass transition temperature of the polyphenylene ether, (2) a method of melt-kneading and reacting with a modified compound at a temperature in the range of the glass transition temperature of the polyphenylene ether or higher and 360 °C or lower, (3) a method of reacting the polyphenylene ether and the modified compound in a solution at a temperature lower than the glass transition temperature of the polyphenylene ether, etc. can be mentioned. From the viewpoint of productivity, the method (1) or (2) is preferable.

[0027] Next, the modifying compounds used for producing the modified polyphenylene ether will be described.

[0028] Examples of the modifying compound having a carbon-carbon double bond in the molecule and simultaneously having a carboxylic acid group or an acid anhydride group include, but are not limited to, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, chloromaleic acid, and cis-4-cyclohexene-1,2-dicarboxylic acid, and acid anhydrides thereof. In particular, from the viewpoint of reactivity with polyphenylene ether-based resins, fumaric acid, maleic acid, and maleic anhydride are preferred, and fumaric acid and maleic anhydride are more preferred.

[0029] In addition, a compound in which one or two of the two carboxyl groups of the above unsaturated dicarboxylic acid are esterified can also be used as the modifying compound.

[0030] Examples of the modifying compound having a carbon-carbon double bond in the molecule and simultaneously having a glycidyl group include, but are not limited to, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxidized natural oils, etc. Among these, glycidyl acrylate and glycidyl methacrylate are preferred.

[0031] Examples of the modifying compound having a carbon-carbon double bond in the molecule and simultaneously having a hydroxy group include, but are not limited to, allyl alcohol, 4-penten-1-ol, 1,4-pentadien-3-ol, etc., unsaturated alcohols of the general formula C n H 2n-1 OH, C n H 2n-3 OH (wherein n is a positive integer), unsaturated alcohols of the general formula C n H 2n-5 OH, C n H 2n-7 OH (wherein n is a positive integer), etc.

[0032] The above-described modifying compounds may be used alone or in combination of two or more.

[0033] When producing the modified polyphenylene ether, the addition amount of the modifying compound is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the polyphenylene ether, from the viewpoint of, for example, the efficiency of modification.

[0034] When producing the modified polyphenylene ether using a radical initiator, the addition amount of the radical initiator is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.5 part by mass, and still more preferably 0.05 to 0.3 part by mass with respect to 100 parts by mass of the polyphenylene ether, from the viewpoints of the modification rate and the balance of physical properties.

[0035] In addition, the addition rate of the modifying compound to the modified polyphenylene ether is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass with respect to 100% by mass of the modified polyphenylene ether.

[0036] In the modified polyphenylene ether, unreacted modifying compound and polymer of the modifying compound may remain. When unreacted modifying compound and polymer of the modifying compound remain, the amount is preferably less than 5% by mass, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

[0037] · Component (a-2) In the present embodiment, the (a-2) styrene resin is a copolymer obtained by polymerizing a styrene compound or a styrene compound and a compound copolymerizable with the styrene compound (hereinafter sometimes simply referred to as "copolymerizable compound") in the presence or absence of a rubbery polymer. The styrene resin corresponding to the (b) hydrogenated block copolymer described later is not the (a-2) component but the (b) component.

[0038] Examples of the styrene compound include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, etc. Among them, styrene is preferred.

[0039] Examples of the copolymerizable compound include, but are not limited to, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; acid anhydrides such as maleic anhydride, etc.

[0040] The amount of the copolymerizable compound used is preferably 20% by mass or less, more preferably 15% by mass or less, based on 100% by mass of the total amount with the styrene compound.

[0041] Examples of the rubbery polymer include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, ethylene-propylene copolymer rubbers, etc. Among them, polybutadiene, styrene-butadiene random copolymers, styrene-butadiene block copolymers, and rubber components obtained by partially, substantially completely or completely hydrogenating these (for example, rubber components with a hydrogenation rate of 50 to 100%) are preferred.

[0042] Examples of the component (a-2) include, but are not limited to, homopolymer polystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubbery polymer-acrylonitrile copolymer (ABS resin), and other styrene copolymers, etc. Among them, from the viewpoint of compatibility with the polyphenylene ether resin, the component (a-2) is preferably at least one selected from the group consisting of homopolymer polystyrene and rubber-modified polystyrene (HIPS).

[0043] · Component (b) The resin composition of this embodiment contains (b) a hydrogenated block copolymer.

[0044] The hydrogenated block copolymer (b) of the present embodiment is a block copolymer of an aromatic vinyl compound (e.g., styrene) and a conjugated diene compound, that is, a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polystyrene block and a conjugated diene compound polymer block.

[0045] From the viewpoint of heat resistance stability, the hydrogenation rate (hydrogenation ratio) of the unsaturated bonds derived from the conjugated diene compound by hydrogenation is preferably 60% or more, more preferably 80% or more, and still more preferably 95% or more.

[0046] As the structure of the block copolymer before hydrogenation, when the block copolymer is a block copolymer of styrene and a conjugated diene compound, if the styrene block chain is represented by S and the diene compound block chain is represented by B, for example, S-B-S, S-B-S-B, (S-B-)4-S, S-B-S-B-S, etc. can be mentioned.

[0047] In addition, the microstructure of the polymer block of the conjugated diene compound (the bonding form of the conjugated diene compound) can be arbitrarily selected. The vinyl bond amount (the total of 1,2-vinyl bonds and 3,4-vinyl bonds) of the conjugated diene compound polymer block is preferably 2 to 60%, more preferably 8 to 40% with respect to the total bond amount of the conjugated diene compound polymer (the total of 1,2-vinyl bonds, 3,4-vinyl bonds, and 1,4-conjugated bonds).

[0048] The number average molecular weight of the component (b) is preferably 100,000 to 400,000, more preferably 150,000 to 350,000, and still more preferably 200,000 to 300,000. When the number average molecular weight of the component (b) is 100,000 or more, a resin composition excellent in impact resistance can be obtained. The impact resistance of the resin composition of the present embodiment improves in proportion to the number average molecular weight of the component (b). Also, when the number average molecular weight of the component (b) is 400,000 or less, a resin composition with a low load during melt extrusion, excellent processing fluidity, and excellent dispersibility of the component (b) in the resin composition can be obtained.

[0049] (b) component, when having a styrene polymer block chain, preferably has at least one styrene polymer block chain with a number average molecular weight of 15,000 or more. More preferably, it is 20,000 to 50,000. Even more preferably, the number average molecular weight of all styrene polymer block chains is 15,000 or more.

[0050] (b) component, when having a styrene polymer block chain, the proportion occupied by the styrene polymer block chain of (b) component is not particularly limited as long as the number average molecular weight of the styrene polymer block chain is within the above range, but from the viewpoint of impact resistance, it is preferably 10 to 70% by mass, more preferably 20 to 50% by mass, and even more preferably 30 to 40% by mass.

[0051] As (b) component, two or more kinds of hydrogenated block copolymers having different compositions or structures can also be used in combination. For example, a combination of a hydrogenated block copolymer having a bound styrene polymer block content of 50% by mass or more and a hydrogenated block copolymer having a bound styrene polymer block content of 30% by mass or less, a combination of hydrogenated block copolymers having different molecular weights, and a hydrogenated random block copolymer obtained by hydrogenating a block copolymer containing a block copolymer of styrene and a conjugated diene compound and a random copolymer block of styrene and a conjugated diene compound as described above.

[0052] The "bound styrene polymer block content" refers to the proportion occupied by the styrene polymer block chain in (b) component.

[0053] ·(c) component The (c) component contained in the resin composition of this embodiment may be any organic phosphate ester generally used as a flame retardant.

[0054] (c) component may be only one kind or a combination of two or more kinds.

[0055] (c) components include, but are not limited to, for example, triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol bis[di(2,6-dimethylphenyl) phosphate], 2,2-bis{4-[bis(phenoxy)phosphoryloxy]phenyl}propane, 2,2-bis{4-[bis(methylphenoxy)phosphoryloxy]phenyl}propane, etc. Further, as the (c) component, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyldiphenyl phosphate, diisopropylphenyl phosphate and other phosphate ester flame retardants; diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphonate, diphenyl-4-hydroxy-3,5-dibromobenzyl phosphonate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(chloropropyl) phosphate, bis(2,3-dibromopropyl)-2,3-dichloropropyl phosphate, tris(2,3-dibromopropyl) phosphate, bis(chloropropyl) monooctyl phosphate, hydroquinonyl diphenyl phosphate, phenyl nonylphenyl hydroquinonyl phosphate, phenyldinonylphenyl phosphate and other monophosphate ester compounds; and aromatic condensed phosphate ester compounds, etc. Among these, aromatic condensed phosphate ester compounds are preferred because they generate less gas during processing and have excellent thermal stability, etc.

[0056] Aromatic condensed phosphate ester compounds are commercially available and include, but are not limited to, for example, the trade names "CR741", "CR733S", "PX200", "E890" of Daihachi Chemical Industry Co., Ltd., and the trade names "FP600", "FP700", "FP800" of ADEKA Corporation, etc.

[0057] As the component (c) used in this embodiment, an aromatic condensed phosphate ester represented by the following general formula (I) or the following general formula (II) is preferable, and an aromatic condensed phosphate ester represented by the general formula (I) is more preferable. [Chemical formula] [Chemical formula] In the general formula (I), Q1, Q2, Q3, and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms, R11 and R12 represent a methyl group, and R13 and R14 each independently represent a hydrogen atom or a methyl group. In the general formula (II), Q1, Q2, Q3, and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms, and R11 and R12 represent a methyl group. y is an integer of 1 or more, n1 and n2 each independently represent an integer of 0 to 2, and m1, m2, m3, and m4 each independently represent an integer of 0 to 3.

[0058] In the general formulas (I) and (II), y is preferably an integer of 1, 2, or 3, and more preferably 1.

[0059] In an example of the preferable general formula (I), m1, m2, m3, m4, n1, and n2 are 0, R13 and R14 are methyl groups, and y is 1, 2, or 3. In another example of the preferable general formula (I), Q1, Q2, Q3, Q4, R13, and R14 are methyl groups, n1 and n2 are 0, m1, m2, m3, and m4 are 1, 2, or 3, and y is 1, 2, or 3.

[0060] In the component (c), it is preferable to contain 50 to 100% by mass of the aromatic condensed phosphate ester of the formula (I) with respect to 100% by mass of the component (c).

[0061] In one example of the preferred general formula (II), m1, m2, m3, m4, n1, and n2 are 0, and y is 1, 2, or 3. In another example of the preferred general formula (II), Q1, Q2, Q3, and Q4 are methyl groups, n1 and n2 are 0, m1, m2, m3, and m4 are 1, 2, or 3, and y is 1, 2, or 3.

[0062] (c) It is preferable that the aromatic condensed phosphate ester of formula (II) is contained in an amount of 50 to 100% by mass based on 100% by mass of component (c).

[0063] The aromatic condensed phosphate ester compound more preferably has an acid value of 0.1 or less (a value obtained in accordance with JIS K2501).

[0064] · Component (d) (d) Component is a polymer obtained by polymerizing monomer units containing olefins (e.g., α-olefins). Examples of component (d) include homopolymers of ethylene, propylene, and other olefinic hydrocarbons, and copolymers thereof. Component (d) may be only one type or a combination of two or more types. Examples of component (d) include polyethylene such as low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polybutene, etc. Preferred examples of component (d) include polyethylene and polypropylene from the viewpoints of oil resistance and impact resistance.

[0065] The melt flow rate of component (d) is 30 g / 10 min or more, preferably 40 g / 10 min or more, and more preferably 50 g / 10 min or more. The MFR of component (d) is preferably 200 g / 10 min or less, more preferably 150 g / 10 min or less, and even more preferably 100 g / 10 min or less. By setting the MFR of component (d) to 30 g / 10 min or more, the polyolefin resin tends to be present in the surface portion (e.g., within 2 μm from the surface) of the molded article of the resin composition, and the oil resistance is excellent.

[0066] When the component (d) is polyethylene, it is appropriate to measure the MFR under the conditions of a temperature of 190°C and a load of 2.16 kg. In one embodiment, the MFR (190°C, 2.16 kg) of polyethylene is 30 g / 10 min or more, 40 g / 10 min or more, 50 g / 10 min or more. In another embodiment, the MFR (190°C, 2.16 kg) of polyethylene is 200 g / 10 min or less, 150 g / 10 min or less, 100 g / 10 min or less. By setting the MFR (190°C, 2.16 kg) of polyethylene to 30 g / 10 min or more, the polyolefin resin is likely to be present in the surface portion (for example, within 2 μm from the surface) of the molded body of the resin composition. In particular, when the MFR (190°C, 2.16 kg) of polyethylene is 100 g / 10 min or less, the flame retardancy of the resin composition tends to be significantly improved.

[0067] When the component (d) is polypropylene, it is appropriate to measure the MFR under the conditions of a temperature of 230°C and a load of 2.16 kg. In one embodiment, the MFR (230°C, 2.16 kg) of polypropylene is 30 g / 10 min or more, 40 g / 10 min or more, 50 g / 10 min or more. In another embodiment, the MFR (230°C, 2.16 kg) of polypropylene is 200 g / 10 min or less, 150 g / 10 min or less, 100 g / 10 min or less. By setting the MFR (230°C, 2.16 kg) of polypropylene to 30 g / 10 min or more, the polyolefin resin is likely to be present in the surface portion (for example, within 2 μm from the surface) of the molded body of the resin composition.

[0068] In one embodiment, the amount of polyethylene wax in the component (d) is more than 0% by mass and 5% by mass or less.

[0069] · Other flame retardants Various conventionally known flame retardants and flame retardant aids may be added to the resin composition of this embodiment. Examples of other flame retardants include phosphinates, alkaline earth metal hydroxides such as magnesium hydroxide, aluminum hydroxide, alkali metal hydroxides, zinc borate compounds, zinc stannate compounds, and the like.

[0070] · Additives In order to impart further other properties to the resin composition of the present embodiment, additives such as resins other than the components (a), (b), and (d), plasticizers, antioxidants, and stabilizers such as ultraviolet absorbers, antistatic agents, mold release agents, dyes, pigments, fillers, reinforcing materials, and spreading agents can be added within a range that does not impair the effects of the present invention.

[0071] · Content of each component In the resin composition of the present embodiment, the amounts of the components (a) to (d) are such that, with respect to a total of 100 parts by mass of the components (a) and (b), the amount of the component (a) is 60 to 90 parts by mass, the amount of the component (b) is 10 to 40 parts by mass, the amount of the component (c) is 8 to 25 parts by mass, and the amount of the component (d) is 1 to 10 parts by mass.

[0072] In the resin composition of the present embodiment, from the viewpoints of flame retardancy and oil resistance, the contents of the components (a) and (b) are preferably (a) component: 65 to 90 parts by mass and (b) component: 10 to 35 parts by mass, more preferably (a) component: 65 to 85 parts by mass and (b) component: 15 to 35 parts by mass, and even more preferably (a) component: 70 to 85 parts by mass and (b) component: 15 to 30 parts by mass, with respect to a total of 100 parts by mass of the components (a) and (b). Specifically, when the amount of the component (a) is 60 parts by mass or more, it tends to be excellent in flame retardancy and rigidity, and when the amount of the component (b) is 10 parts by mass or more, it tends to be excellent in oil resistance and impact resistance.

[0073] The component (a) may be only the component (a-1) or a mixed resin of the component (a-1) and the component (a-2).

[0074] (a) When the component is a mixed resin of (a-1) component and (a-2) component, with respect to 100 parts by mass of the mixed resin, the amount of the (a-1) component is 55 to 99.95 parts by mass, and the amount of the (a-2) component is 0.05 to 45 parts by mass. When the amount of the (a-1) component is 55 parts by mass or more, it tends to have excellent flame retardancy. In particular, to obtain a resin composition with excellent flame retardancy, it is preferable that the (a) component is only the (a-1) component. Alternatively, to obtain a resin composition with excellent flame retardancy, it is preferable that the (a) component is a mixed resin, and with respect to 100 parts by mass of the mixed resin, the amount of the (a-1) component is preferably 60 to 99.95 parts by mass, more preferably 65 to 99.95 parts by mass, and even more preferably 85 to 95 parts by mass.

[0075] (c) From the viewpoints of flame retardancy and oil resistance, the content of the (c) component is 8 to 25 parts by mass with respect to 100 parts by mass in total of the (a) component and the (b) component. Preferably it is 10 to 21 parts by mass, and more preferably 10 to 20 parts by mass. When the amount of the (c) component is 8 parts by mass or more, it tends to have excellent flame retardancy, and when it is 25 parts by mass or less, it tends to have excellent oil resistance.

[0076] (d) From the viewpoints of flame retardancy and oil resistance, the content of the (d) component is 1 to 10 parts by mass with respect to 100 parts by mass in total of the (a) component and the (b) component. Preferably it is 2 to 8 parts by mass, and more preferably 3 to 7 parts by mass. When the (d) polyolefin resin is 1 part by mass or more, it tends to have excellent oil resistance, and when it is 10 parts by mass or less, it tends to have excellent flame retardancy.

[0077] When other flame retardants are included, from the viewpoints of fluidity and appearance, the content of the other flame retardants is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less with respect to 100 parts by mass in total of the (a) component and the (b) component. When the content of the other flame retardants is 40 parts by mass or less, it tends to have excellent fluidity and appearance.

[0078] The content of the above-mentioned total additives is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less with respect to 100% by mass in the resin composition.

[0079] ·Morphology Regarding the morphology of the resin composition of this embodiment, from the viewpoint of flame retardancy, the phase containing the component (a) forms a continuous phase. This morphology can be determined by dyeing with a known dyeing agent such as ruthenium tetroxide or osmium tetroxide according to the type of thermoplastic resin, and observing an image at a magnification of 10,000 times using a transmission microscope or the like.

[0080] (Method for producing resin composition) The resin composition of this embodiment can be produced, for example, by melt-kneading the components (a) to (d) and the like using a twin-screw extruder.

[0081] Examples of the twin-screw extruder include the product name "ZSK" series manufactured by Coperion, the product name "TEM" series manufactured by Toshiba Machine Co., Ltd., and the product name "TEX" series manufactured by Japan Steel Works, Ltd.

[0082] In the method for producing the resin composition of this embodiment, the melt-kneading temperature and the screw rotation speed can be appropriately selected from the ranges of a melt-kneading temperature of 100 to 370°C and a screw rotation speed of 100 to 1200 rpm.

[0083] Examples of the raw material supply device for supplying raw materials to the twin-screw extruder include a loss-in-weight feeder, a single-screw feeder, a twin-screw feeder, a table feeder, a rotary feeder, etc. Among them, from the viewpoint of less variation error in raw material supply, a loss-in-weight feeder is preferred.

[0084] (Molded article) By molding the resin composition of this embodiment, a molded article can be obtained. The molded article contains at least the resin composition of this embodiment.

[0085] As the molding method, for example, known molding methods such as injection molding, blow molding, extrusion molding, sheet molding, film molding, etc. can be used, and injection molding is particularly preferred. Examples of injection molding machines include the product name "SH100C" manufactured by Sumitomo Heavy Industries, Ltd.

[0086] In the molding method of the resin composition of the present embodiment, the melting temperature and mold temperature can be appropriately selected from the range of a melting temperature of 200 to 320 °C and a mold temperature of 30 to 100 °C.

[0087] The molded body can be used as various molded bodies and can be utilized in a wide range of fields such as industrial parts, electrical and electronic parts, office equipment housings, automotive parts, precision parts, etc. In particular, it can be suitably used for connection structures for solar power generation modules such as connectors for solar power generation modules and junction boxes for solar cells.

[0088] (Connection structure for solar power generation module) The connection structure for solar power generation module of the present embodiment includes the molded body of the resin composition of the present embodiment.

[0089] (Junction box for solar power generation module) The junction box for solar power generation module of the present embodiment includes the molded body of the resin composition of the present embodiment.

Examples

[0090] Hereinafter, the present invention will be described in detail with specific examples and comparative examples, but the present invention is not limited to the following examples.

[0091] The raw materials used in the resin compositions of the examples and comparative examples are shown below. · Component (a) Component (a-1): Poly(2,6-dimethyl-1,4-phenylene ether) with a reduced viscosity of 0.5 dL / g Component (a-2): Rubber-modified polystyrene (HIPS), manufactured by petrochemical, product name "CT60", content of rubbery polymer: 10% by mass

[0092] · Component (b) Manufactured by TSRC, trade name "TAIPOL6151", number average molecular weight: about 280,000

[0093] · Component (c) Component (c-1): Manufactured by Daihachi Chemical Industry Co., Ltd., trade name "E890", aromatic condensed phosphate ester compound

[0094] · Component (d) Component (d-1): Polypropylene with MFR (230°C, 2.16 kg) of 100 g / 10 min Component (d-2): Low density polyethylene with MFR (190°C, 2.16 kg) of 55 g / 10 min Component (d-3): Polypropylene with MFR (230°C, 2.16 kg) of 0.4 g / 10 min Component (d-4): Low density polyethylene with MFR (190°C, 2.16 kg) of 0.4 g / 10 min Component (d-5): Low density polyethylene with MFR (190°C, 2.16 kg) of 20 g / 10 min

[0095] Other flame retardant: Manufactured by Clariant, trade name "Exolit® OP 930"

[0096] Other materials used in the examples are shown below. Processing oil: Manufactured by Nippon Kogyo Oil Co., Ltd., trade name "G-6280"

[0097] The apparatuses used in the examples are shown below. Twin-screw extruder: Manufactured by Coperion, trade name "ZSK-25WLE" Small injection molding machine: Manufactured by Sumitomo Heavy Industries, Ltd., trade name "SH100C" Microscope: Manufactured by Keyence Corporation, trade name "VHX-5000" Transmission electron microscope (TEM): Manufactured by Hitachi High-Technologies Corporation, trade name "HT7700"

[0098] (Examples 1 to 6, Comparative Examples 1 to 11) A twin-screw extruder was fed with components (a) to (d) and other flame retardants in the compositions shown in Tables 1 and 2, and melt-kneaded under the conditions of an extrusion temperature of 300 to 320 °C, a screw rotation speed of 300 rpm, and a discharge rate of 15 kg / hour to obtain pellets of the resin composition. The settings of the twin-screw extruder were as follows: the number of barrels was 12 blocks. Regarding the flow direction of the raw materials, an upstream supply port was provided at the first barrel from the upstream, a liquid addition pump was provided at the seventh barrel, and vacuum vents were provided at the fifth barrel and the eleventh barrel.

[0099] The measurement methods of physical properties in the examples and comparative examples are shown below.

[0100] · Oil resistance The resin composition pellets were supplied to a small injection molding machine set at a cylinder temperature of 280 °C, and a flat plate of 120 mm × 80 mm × 3 mm was molded under the condition of a mold temperature of 80 °C. From this flat plate, a strip-shaped (80 mm × 12.5 mm × 3 mm) test piece was cut out such that the longitudinal direction was perpendicular to the flow direction. Regarding this test piece, with the horizontal direction as the x-axis and the vertical direction as the y-axis, it was attached using a jig onto the curved surface of a bending bar having a parabola shaped according to the equation y 2 = 6x (x ≥ 0, y ≥ 0) so that there was no gap between the bar and the test piece. Also, for the bending bar, the position where x = 0 and y = 0 on its vertical cross-section was set as the arrangement position of the measurement starting point side end of the test piece, and the position where x > 0 and y > 0 was set as the arrangement position of the measurement end point side end of the test piece.

[0101] Next, processing oil was applied to the surface of the test piece and left for 24 hours under the condition of 40 °C. When cracks occurred on the surface of the test piece after 24 hours, the critical position (the position where the value of x was the largest in the x-axis direction of the bending bar) where the cracks occurred was read.

[0102] The critical position where cracks occur is read by transcribing the scale of the x-axis coordinate of the bending bar onto the test piece while it is attached to the bending bar, and after removing the test piece from the bending bar, checking for the presence of cracks and comparing with the transcribed scale at the position where the cracks exist. (Since the critical position corresponds to the x-axis coordinate of the bending bar, it is not the peripheral length of the test piece). In the present disclosure, a crack is a crack with a length of 200 μm or more in the flow direction that can be seen when observing the surface of the test piece using a microscope).

[0103] Then, the critical strain (%) was calculated from the thickness of the test piece and the critical position where cracks occurred using the following formula. Taking the critical strain (%) of Comparative Example 1 as 100, the critical strains of each Example and Comparative Example were indexed. It was determined that the higher the index value, the better the oil resistance. Critical strain (%) = d × 3 1 / 2 / 2(3 + 2x) 3 / 2 × 100 d: Thickness of the test piece (inch) x: Critical position where cracks occur (inch)

[0104] · Flame retardancy Based on the UL-94 vertical burning test, the flame retardancy was evaluated using an injection-molded test piece with a thickness of 0.75 mm.

[0105] First, the resin composition pellets were supplied to a small injection molding machine with the cylinder temperature set at 300°C to 320°C, and injection molding was performed under the conditions of an injection speed of 20%, an injection pressure of 99%, and a mold temperature of 90°C to mold 5 test pieces with the dimensions (length 125 mm × width 13 mm, thickness 0.75 mm) specified by the standard.

[0106] The flame of a gas burner was applied to the test piece to evaluate the degree of combustion. Note that the flame retardancy grade indicates the class of flame retardancy classified by the UL94 vertical test. The test was performed 5 times for all test pieces for determination. The outline of the classification method is as follows. Flame retardancy evaluation criteria V-0 (Qualified): Meeting all of the total combustion time of 5 pieces being 50 seconds or less, the maximum combustion time being 10 seconds or less, and no flaming dripping Vout: Meeting any one or more of the total combustion time of 5 pieces being over 250 seconds, the maximum combustion time being over 30 seconds, and having flaming dripping

[0107] · Morphology Ultra-thin sections with a thickness of several 10 to 100 nm were prepared from a molded body produced in the same manner as the test piece for oil resistance evaluation using an ultramicrotome. Thereafter, staining was performed using osmium tetroxide and ruthenium tetroxide, and the stained ultra-thin sections were observed using a transmission electron microscope to obtain an image at a magnification of 10,000 times. From the obtained image, it was determined whether the phase containing the (a) component formed a continuous phase.

[0108] When observing the morphology of the molded bodies produced from the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 11, in all cases, the phase containing the (a) component formed a continuous phase.

[0109]

Table 1

[0110]

Table 2

[0111] All of Examples 1 to 6 were excellent in oil resistance and flame retardancy, and the resin composition according to this embodiment was able to mold a molded body that achieved both high oil resistance and flame retardancy.

Industrial Applicability

[0112] The resin composition of the present invention can be used for molded bodies that require high oil resistance and flame retardancy.

Claims

1. (a) A polyphenylene ether resin, or a mixed resin of (a-1) polyphenylene ether resin and (a-2) styrene resin, (b) A hydrogenated block copolymer, (c) A phosphate ester compound, and (d) A polyolefin resin, wherein, with respect to a total of 100 parts by mass of the component (a) and the component (b), the amount of the component (a) is 60 to 90 parts by mass, the amount of the component (b) is 10 to 40 parts by mass, the amount of the component (c) is 8 to 25 parts by mass, the amount of the component (d) is 1 to 10 parts by mass, when the component (a) is the mixed resin, with respect to 100 parts by mass of the mixed resin, the amount of the (a-1) polyphenylene ether resin is 55 to 99.95 parts by mass, the melt flow rate of the component (d) is 30 g / 10 min or more, A resin composition in which the phase containing the component (a) forms a continuous phase.

2. The resin composition according to claim 1, wherein the amount of the component (c) is 10 to 20 parts by mass with respect to a total of 100 parts by mass of the component (a) and the component (b).

3. The resin composition according to claim 1 or 2, wherein the amount of the component (d) is 2 to 8 parts by mass with respect to a total of 100 parts by mass of the component (a) and the component (b).

4. The resin composition according to any one of claims 1 to 3, wherein the component (c) is a phosphate ester compound represented by the following general formula (I) or general formula (II). 【Chemical 1】 【Chemical 2】 (In general formula (I), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, R11 and R12 represent a methyl group, and R13 and R14 independently represent a hydrogen atom or a methyl group. In general formula (II), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, and R11 and R12 represent a methyl group. y is an integer of 1 or more, n1 and n2 independently represent an integer of 0 to 2, and m1, m2, m3, and m4 independently represent an integer of 0 to 3.)

5. A connection structure for a solar power generation module, including a molded body of the resin composition according to any one of claims 1 to 4.

6. A junction box for a solar power generation module, including a molded body of the resin composition according to any one of claims 1 to 4.

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