JP7709910B2 - Resin composition, connection structure for photovoltaic power generation module, and junction box for photovoltaic power generation module - Google Patents

Description

The present invention relates to a resin composition, a connection structure for a photovoltaic power generation module, and a junction box for a photovoltaic power generation module.

Traditionally, polyphenylene ether resins have been widely used in electrical and electronic components used in secondary batteries or solar power generation, as well as in home appliances and office equipment, due to their excellent electrical insulation properties, heat resistance, hydrolysis resistance, and flame retardancy.

On the other hand, polyphenylene ether resin compositions do not have sufficient oil resistance, and when they come into contact with rust inhibitors attached to the molds of molding machines or with lubricating oils for various application parts, cracks or breakage can occur, which is often a problem.

To address this issue, for example, Patent Document 1 describes a resin composition made of a polypropylene resin and a polyphenylene ether resin, which has a polypropylene resin as the continuous phase, and which has excellent heat resistance, flame retardancy, and oil resistance.

JP 2000-344974 A

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

Therefore, the objective of the present invention is to provide a resin composition that combines high oil resistance and flame retardancy.

As a result of intensive research to solve the above problems, the inventors discovered that the above problems can be advantageously solved by setting the content of each component in a specific range and forming a continuous phase containing component (a) 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, and thus completed the present invention.

That is, the present invention is as follows.
First aspect: (a) (a-1) a polyphenylene ether-based resin, or a mixed resin of (a-1) a polyphenylene ether-based resin and (a-2) a styrene-based resin;
(b) a hydrogenated block copolymer; and
(c) a phosphate ester compound; and
(d) a polyolefin resin; and
Including,
Relative to a total of 100 parts by mass of the component (a) and the component (b),
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 component (a) is the mixed resin, the amount of the polyphenylene ether resin (a-1) is 55 to 99.95 parts by mass per 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 a phase containing the component (a) 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 per 100 parts by mass of the total of the (a) component and the (b) component.
A third aspect: The resin composition according to the first or second aspect, wherein the amount of the (d) component is 2 to 8 parts by mass per 100 parts by mass of the total of the (a) component and the (b) component.
A fourth aspect: The resin composition according to any one of the first to third aspects, wherein the component (c) is a phosphoric acid ester compound represented by the following general formula (I) or general formula (II):
(In general formula (I), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, R11 and R12 independently represent a methyl group, and R13 and R14 independently represent a hydrogen atom or a methyl group.
In formula (II), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, and R11 and R12 each 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.
Fifth aspect: A connection structure for a photovoltaic power generation module, comprising a molded body of the resin composition according to any one of the first to fourth aspects.
Sixth aspect: A junction box for a photovoltaic power generation module, comprising a molded body of the resin composition according to any one of the first to fourth aspects.

The present invention makes it possible to obtain a resin composition that combines high oil resistance and flame retardancy.

The following describes in detail the form for carrying out the present invention (hereinafter referred to as the "present embodiment"). The following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out with appropriate modifications within the scope of its gist.

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. In this embodiment, component (a-1) alone, or component (a-1) and component (a-2) collectively, may be referred to as component (a).

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 into standard polystyrene.

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 for each resin, the measurement load for MFR is 2.16 kg. For example, the measurement conditions for 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. In addition, for example, MFR (230°C, 2.16 kg) means MFR measured under conditions of a temperature of 230°C and a load of 2.16 kg. It is desirable to select an appropriate temperature for the measurement temperature of the melt flow rate depending on the type of resin to be measured, for example, 230°C for polypropylene and 190°C for polyethylene. In addition, when component (d) is composed of multiple different polyolefin resins, the measurement temperature is the measurement temperature of 50% or more of the polyolefin resins relative to the total mass of the polyolefin resins.

Resin Composition The resin composition of the present embodiment is
(a) (a-1) a polyphenylene ether-based resin or a mixed resin of (a-1) a polyphenylene ether-based resin and (a-2) a styrene-based resin;
(b) a hydrogenated block copolymer; and
(c) a phosphate ester compound; and
(d) a polyolefin resin; and
Including,
Relative to a total of 100 parts by mass of the component (a) and the component (b),
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 component (a) is the mixed resin, the amount of the polyphenylene ether resin (a-1) is 55 to 99.95 parts by mass per 100 parts by mass of the mixed resin,
The melt flow rate of the (d) component is 30 g/10 min or more,
The resin composition is one in which the phase containing the component (a) forms a continuous phase.

Component (a) The component (a) of the present embodiment is (a-1) a polyphenylene ether-based resin, or a mixture of (a-1) a polyphenylene ether-based resin and (a-2) a styrene-based resin.

Component (a) may be of only one type or of a combination of two or more types.

Component (a-1) As the component (a-1) contained in the resin composition of the present embodiment, either a homopolymer consisting of a structural unit of the following general formula (III) or a copolymer having a structural unit of the general formula (III) (hereinafter, sometimes simply referred to as "polyphenylene ether") can be used.
In general formula (III), O is an oxygen atom, and R21 to R24 independently represent any one selected from the group consisting of a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 8 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbyloxy group, and a halohydrocarbyloxy group (wherein at least two carbon atoms separate the halogen atom from the oxygen atom).

Examples of homopolymers of polyphenylene ether resins 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), etc.

Examples of copolymers of polyphenylene ether resins include, but are not limited to, copolymers of 2,6-dimethylphenol and other phenols (e.g., copolymers with 2,3,6-trimethylphenol, copolymers with 2-methyl-6-butylphenol).

Among these, polyphenylene ether resins are preferably poly(2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or a mixture of these, from the viewpoints of balance of mechanical properties and productivity.

The method for producing the polyphenylene ether resin used in this embodiment is not limited to the following, but examples thereof include known production methods described in U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357, and 3,257,358, JP-A-50-51197, JP-B-52-17880, and JP-A-63-152628, etc.

From the viewpoint of the balance between molding flowability and physical properties, the reduced viscosity of the polyphenylene ether resin is preferably in the range of 0.30 to 0.65 dL/g. More preferably, it is in the range of 0.40 to 0.60 dL/g, and even more preferably, it is in the range of 0.45 to 0.55 dL/g. If the reduced viscosity is 0.30 dL/g or more, the impact strength or oil resistance is excellent. Also, if the reduced viscosity is 0.65 dL/g or less, the molding flowability is excellent. In this embodiment, the reduced viscosity of the polyphenylene ether resin is a value measured using a 0.5 g/dL chloroform solution at 30°C using an Ubbelohde type viscometer.

In this embodiment, a mixture of two or more polyphenylene ether resins having different reduced viscosities can also be preferably used.

The polyphenylene ether resin (a-1) of this embodiment may also contain a modified polyphenylene ether that has been modified in whole or in part. The modified polyphenylene ether referred to here refers to a polyphenylene ether that has at least one carbon-carbon double bond or triple bond in the molecule and has at least one group selected from the group consisting of a carboxylic acid group, an acid anhydride group, an amino group, a hydroxyl group, and a glycidyl group (hereinafter, may be simply referred to as a "modified compound"). Only one type of modified compound may be used, or two or more types may be used in combination.

Methods for producing modified polyphenylene ether include, but are not limited to, (1) a method of reacting with a modifying compound at a temperature in the range of 100°C or higher and lower than the glass transition temperature of polyphenylene ether, (2) a method of melt-kneading and reacting with a modifying compound at a temperature in the range of higher than the glass transition temperature of polyphenylene ether and lower than 360°C, and (3) a method of reacting polyphenylene ether with a modifying compound in a solution at a temperature lower than the glass transition temperature of polyphenylene ether, in the presence or absence of a radical initiator. From the viewpoint of productivity, method (1) or (2) is preferred.

Next, we will explain the modifying compound used to produce modified polyphenylene ether.

Modified compounds 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, as well as their acid anhydrides. In particular, from the viewpoint of reactivity with polyphenylene ether resins, fumaric acid, maleic acid, and maleic anhydride are preferred, with fumaric acid and maleic anhydride being more preferred.

In addition, compounds in which one or two of the two carboxyl groups of the above unsaturated dicarboxylic acid are esterified can also be used as modified compounds.

Modified compounds having a carbon-carbon double bond and a glycidyl group in the molecule include, but are not limited to, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxidized natural fats and oils, etc. Among these, glycidyl acrylate and glycidyl methacrylate are preferred.

Examples of modified compounds having a carbon-carbon double bond and a hydroxyl group in the molecule include, but are not limited to, unsaturated alcohols of the general formula C _n H _2n-1 OH, C _n H _{2n-3 OH (wherein n is a positive integer), such as allyl alcohol, 4-penten-1-ol, and 1,4-pentadiene} -3-ol, and unsaturated alcohols of the general formula C _n H _2n-5 OH, C _n H _2n-7 OH (wherein n is a positive integer).

The above-mentioned modified compounds may be used alone or in combination of two or more.

The amount of the modifying compound added when producing modified polyphenylene ether is, for example, preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of polyphenylene ether, from the viewpoint of modification efficiency.

When producing modified polyphenylene ether using a radical initiator, the amount of radical initiator added is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.5 parts by mass, and even more preferably 0.05 to 0.3 parts by mass, per 100 parts by mass of polyphenylene ether, from the viewpoint of the balance between the modification rate and physical properties.

The addition rate of the modifying compound to the modified polyphenylene ether is preferably 0.01 to 5 mass%, more preferably 0.05 to 3 mass%, and even more preferably 0.1 to 1 mass%, relative to 100 mass% of the modified polyphenylene ether.

In the modified polyphenylene ether, unreacted modified compounds and polymers of modified compounds may remain. When unreacted modified compounds and polymers of modified compounds remain, the amount is preferably less than 5% by mass, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

In this embodiment, the (a-2) styrene-based resin is a copolymer obtained by polymerizing a styrene-based compound or a compound copolymerizable with a styrene-based compound (hereinafter, a "compound copolymerizable with a styrene-based compound" may be simply referred to as a "copolymerizable compound") in the presence or absence of a rubber polymer. A styrene-based resin that also corresponds to the (b) hydrogenated block copolymer described below is considered to be the (b) component, not the (a-2) component.

The styrene-based compound includes, but is not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, etc., with styrene being preferred.

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

The amount of the copolymerizable compound used is preferably 20% by mass or less, and more preferably 15% by mass or less, relative to 100% by mass of the total amount of the copolymerizable compound and the styrene-based compound.

Examples of rubbery polymers include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers. Among these, 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.

Examples of the (a-2) component include, but are not limited to, homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin), and other styrene-based copolymers. Among these, from the viewpoint of compatibility with polyphenylene ether-based resins, it is preferable that the (a-2) component is one or more selected from the group consisting of homopolystyrene and rubber-modified polystyrene (HIPS).

Component (b) The resin composition of the present embodiment contains the hydrogenated block copolymer (b).

The (b) hydrogenated block copolymer of this 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 consisting of a polystyrene block and a conjugated diene compound polymer block.

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

When the block copolymer before hydrogenation is a block copolymer of styrene and a conjugated diene compound, examples of the structure of the block copolymer before hydrogenation include S-B-S, S-B-S-B, (S-B-) ₄ -S, S-B-S-B-S, etc., where S is the styrene block chain and B is the diene compound block chain.

The microstructure of the polymer block of the conjugated diene compound (bonding form of the conjugated diene compound) can be selected as desired. The vinyl bond amount (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%, of the total bond amount of the conjugated diene compound polymer (total of 1,2-vinyl bonds, 3,4-vinyl bonds and 1,4-conjugated bonds).

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

When component (b) has a styrene polymer block chain, it is preferable that at least one of the styrene polymer block chains has 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 of the styrene polymer block chains is 15,000 or more.

When component (b) has a styrene polymer block chain, the proportion of the styrene polymer block chain in component (b) 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 mass%, more preferably 20 to 50 mass%, and even more preferably 30 to 40 mass%.

As component (b), two or more hydrogenated block copolymers having different compositions or structures can be used in combination. For example, 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 can be used in combination, hydrogenated block copolymers having different molecular weights can be used in combination, and a block copolymer of styrene and a conjugated diene compound as described above can be used in combination with a hydrogenated random block copolymer obtained by hydrogenating a block copolymer containing a random copolymer block of styrene and a conjugated diene compound.

"Bound styrene polymer block content" refers to the proportion of styrene polymer block chains in component (b).

Component (c) The component (c) contained in the resin composition of the present embodiment may be any organic phosphate ester that is generally used as a flame retardant.

Component (c) may be one type or a combination of two or more types.

Examples of component (c) include, but are not limited to, 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 examples of the component (c) include phosphate ester-based flame retardants such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, and diisopropyl phenyl phosphate; diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphonate, and diphenyl-4-hydroxy-3,5-dibromobenzyl phosphate; Examples of such phosphate ester compounds include monophosphate ester compounds such as phenylphosphonate, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(chloropropyl)phosphate, bis(2,3-dibromopropyl)-2,3-dichloropropylphosphate, tris(2,3-dibromopropyl)phosphate, bis(chloropropyl)monoctylphosphate, hydroquinonyldiphenylphosphate, phenylnonylphenylhydroquinonylphosphate, and phenyldinonylphenylphosphate; and aromatic condensed phosphate ester compounds. Among these, aromatic condensed phosphate ester compounds are preferred because they generate less gas during processing and have excellent thermal stability.

Aromatic condensed phosphate ester compounds are commercially available, and examples include, but are not limited to, the product names "CR741", "CR733S", "PX200", and "E890" from Daihachi Chemical Industry Co., Ltd., and the product names "FP600", "FP700", and "FP800" from ADEKA Corporation.

The component (c) used in this embodiment is preferably an aromatic condensed phosphate ester represented by the following general formula (I) or the following general formula (II), and more preferably an aromatic condensed phosphate ester represented by general formula (I).
In general formula (I), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, R11 and R12 independently 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 independently 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.

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

In one preferred example of 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 preferred example of 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.

It is preferable that component (c) contains 50 to 100 mass% of the aromatic condensed phosphate ester of formula (I) relative to 100 mass% of component (c).

In one preferred example of general formula (II), m1, m2, m3, m4, n1, and n2 are 0, and y is 1, 2, or 3. In another preferred example of 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.

It is preferable that component (c) contains 50 to 100 mass% of the aromatic condensed phosphate ester of formula (II) relative to 100 mass% of component (c).

It is more preferable that the aromatic condensed phosphate ester compound has an acid value of 0.1 or less (a value obtained in accordance with JIS K2501).

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

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 more preferably 100 g/10 min or less. By making the MFR of component (d) 30 g/10 min or more, the polyolefin resin is more likely to be present on the surface portion (e.g., within 2 μm from the surface) of the molded product of the resin composition, resulting in excellent oil resistance.

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

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

In one embodiment, the amount of polyethylene wax in component (d) is greater than 0% by mass and less than or equal to 5% by mass.

Other Flame Retardants The resin composition of the present embodiment may contain various conventionally known flame retardants and flame retardant auxiliaries, such as phosphinates, alkaline earth metal hydroxides such as magnesium hydroxide, aluminum hydroxide, alkali metal hydroxides, zinc borate compounds, and zinc stannate compounds.

Additives In order to impart other properties to the resin composition of the present embodiment, additives such as resins other than the components (a), (b), and (d), plasticizers, antioxidants, stabilizers such as ultraviolet absorbers, antistatic agents, 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.

Content of Each Component In the resin composition of this embodiment, the amounts of the components (a) to (d) are such that, relative to 100 parts by mass of the combined total 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.

In the resin composition of this embodiment, the contents of the (a) and (b) components are, from the viewpoint of flame retardancy and oil resistance, preferably 65 to 90 parts by mass of the (a) component and 10 to 35 parts by mass of the (b) component, more preferably 65 to 85 parts by mass of the (a) component and 15 to 35 parts by mass of the (b) component, and even more preferably 70 to 85 parts by mass of the (a) component and 15 to 30 parts by mass of the (b) component. Specifically, when the amount of the (a) component is 60 parts by mass or more, the flame retardancy and rigidity tend to be excellent, and when the amount of the (b) component is 10 parts by mass or more, the oil resistance and impact resistance tend to be excellent.

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

When the (a) component is a mixed resin of the (a-1) component and the (a-2) component, 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 relative to 100 parts by mass of the mixed resin. When the amount of the (a-1) component is 55 parts by mass or more, the flame retardancy tends to be excellent. 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, the (a) component is a mixed resin, and 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 more preferably 85 to 95 parts by mass relative to 100 parts by mass of the mixed resin.

From the viewpoint of flame retardancy and oil resistance, the content of component (c) is 8 to 25 parts by mass per 100 parts by mass of the total of components (a) and (b). It is preferably 10 to 21 parts by mass, and more preferably 10 to 20 parts by mass. When the amount of component (c) is 8 parts by mass or more, the flame retardancy tends to be excellent, and when it is 25 parts by mass or less, the oil resistance tends to be excellent.

From the viewpoint of flame retardancy and oil resistance, the content of component (d) is 1 to 10 parts by mass per 100 parts by mass of the total of components (a) and (b). It is preferably 2 to 8 parts by mass, and more preferably 3 to 7 parts by mass. When the content of polyolefin resin (d) is 1 part by mass or more, the oil resistance tends to be excellent, and when it is 10 parts by mass or less, the flame retardancy tends to be excellent.

When other flame retardants are included, 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, per 100 parts by mass of the total of components (a) and (b), from the viewpoint of fluidity and appearance. When the content of the other flame retardants is 40 parts by mass or less, the fluidity and appearance tend to be excellent.

The total content of the above-mentioned additives is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, relative to 100% by mass of the resin composition.

Morphology The morphology of the resin composition of the present embodiment is such that the phase containing the component (a) forms a continuous phase from the viewpoint of flame retardancy. This morphology can be determined by staining the resin composition with a known staining agent such as ruthenium tetroxide or osmium tetroxide according to the type of thermoplastic resin, and observing the image at a magnification of 10,000 times using a transmission microscope or the like.

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

Examples of twin-screw extruders include the "ZSK" series manufactured by Coperion, the "TEM" series manufactured by Toshiba Machine Co., Ltd., and the "TEX" series manufactured by Japan Steel Works, Ltd.

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 100 to 370°C and 100 to 1200 rpm.

Examples of raw material supply devices for supplying raw materials to a twin-screw extruder include loss-in-weight feeders, single screw feeders, twin screw feeders, table feeders, rotary feeders, etc., and among these, loss-in-weight feeders are preferred from the viewpoint of less fluctuation error in raw material supply.

(Molded body)
The resin composition of the present embodiment can be molded into a molded article. The molded article contains at least the resin composition of the present embodiment.

As a 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. An example of an injection molding machine is the product name "SH100C" manufactured by Sumitomo Heavy Industries, Ltd.

The melting temperature and mold temperature in the molding method of the resin composition of this embodiment can be appropriately selected from the ranges of 200 to 320°C for the melting temperature and 30 to 100°C for the mold temperature.

The molded article can be used in a variety of applications, including industrial parts, electrical and electronic parts, office equipment housings, automotive parts, and precision parts, and is particularly suitable for use in connection structures for photovoltaic power generation modules, such as photovoltaic power generation module connectors and solar cell junction boxes.

(Connection structure for photovoltaic power generation module)
The connection structure for a photovoltaic power generation module of the present embodiment includes a molded article of the resin composition of the present embodiment.

(Junction box for photovoltaic power generation modules)
The junction box for a photovoltaic power generation module of the present embodiment includes an article molded from the resin composition of the present embodiment.

The present invention will be described in detail below with specific examples and comparative examples, but the present invention is not limited to the following examples.

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) having a reduced viscosity of 0.5 dL/g
Component (a-2): Rubber-modified polystyrene (HIPS), manufactured by Petrochemical, product name "CT60", rubber polymer content: 10% by mass

・Component (b) Manufactured by TSRC, product name "TAIPOL6151", number average molecular weight: approximately 280,000

Component (c) Component (c-1): Daihachi Chemical Industry Co., Ltd., product name "E890", aromatic condensed phosphate ester compound

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

Other flame retardants: Clariant, product name "Exolit (registered trademark) OP 930"

Other materials used in the examples are listed below.
Processing oil: Nippon Kogyo Co., Ltd., product name “G-6280”

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

(Examples 1 to 6, Comparative Examples 1 to 11)
Components (a) to (d) and other flame retardants were fed to a twin-screw extruder in the compositions shown in Tables 1 and 2, and melt-kneaded under 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 a resin composition. The twin-screw extruder was set as follows: the number of barrels was 12 blocks, and in 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 and eleventh barrels.

The methods for measuring physical properties in the examples and comparative examples are shown below.

-Oil resistance The resin composition pellets were fed into a small injection molding machine with a cylinder temperature set to 280 ° C., and a flat plate of 120 mm x 80 mm x 3 mm was molded under the condition of a mold temperature of 80 ° C. From this flat plate, a test piece in a rectangular shape (80 mm x 12.5 mm x 3 mm) was cut out so that the longitudinal direction was perpendicular to the flow direction. The test piece was attached to the curved surface of a bending bar with a parabola shape represented by the equation y ² = 6x (x ≧ 0, y ≧ 0) with the horizontal direction as the x axis and the vertical direction as the y axis, so that no gap was generated between the bar and the test piece, using a jig. In addition, the bending bar is arranged so that the position where x = 0 and y = 0 on the vertical cross section is the position of the measurement starting point side end of the test piece, and the position where x > 0 and y > 0 is the position of the measurement end side end of the test piece.

Next, processing oil was applied to the surface of the test piece and it was left at 40°C for 24 hours. If cracks appeared on the surface of the test piece after 24 hours, the critical position at which the cracks occurred (the position where the x value is the largest in the x-axis direction of the bending bar) was read.

The critical position where cracks occur was read by transferring the x-axis coordinate of the bending bar onto the test piece while it was attached to the bending bar, and then removing the test piece from the bending bar to check for the presence of a crack and compare the position of the crack with the transferred scale (the critical position is the position corresponding to the x-axis coordinate of the bending bar, and is not the periphery length of the test piece). In this disclosure, a crack is a crack of 200 μm or more in the flow direction that can be seen when observing the surface of the test piece using a microscope.

The critical strain (%) was calculated from the thickness of the test piece and the critical position where the crack occurred using the following formula. The critical strain (%) of Comparative Example 1 was set to 100, and the critical strains of each Example and Comparative Example were indexed. The larger the index value, the better the oil resistance was determined to be.
Critical strain (%) = d × 3 ^1/2 /2 (3 + 2x) ^3/2 × 100
d: thickness of test piece (inch)
x: Critical position where cracks occur (inch)

Flame retardancy: Flame retardancy was evaluated using injection molded test pieces having a thickness of 0.75 mm based on the UL-94 vertical flame test.

First, the resin composition pellets were fed into a small injection molding machine with a cylinder temperature set to 300°C to 320°C, and injection molded under conditions of an injection speed of 20%, injection pressure of 99%, and a mold temperature of 90°C to mold five test pieces with the dimensions specified by the standard (length 125 mm x width 13 mm, thickness 0.75 mm).

The flame of a gas burner was applied to the test piece to evaluate the degree of combustion. The flame retardancy grade indicates the flame retardancy class classified by the UL94 vertical test. For each test piece, five tests were performed and a judgment was made. The classification method is as follows:
Flame retardancy evaluation criteria V-0 (pass): Meets all of the following: total burning time of five pieces is 50 seconds or less, maximum burning time is 10 seconds or less, and no flaming drips Vout: Meets one or more of the following: total burning time of five pieces is more than 250 seconds, maximum burning time is more than 30 seconds, and flaming drips

Morphology Ultrathin sections of several tens to 100 nm thick were prepared using an ultramicrotome from molded bodies prepared in the same manner as the test pieces for evaluating oil resistance. The sections were then stained with osmium tetroxide and ruthenium tetroxide, and the stained ultrathin sections were observed using a transmission electron microscope to obtain images at a magnification of 10,000 times. From the images obtained, it was determined whether or not the phase containing component (a) formed a continuous phase.

When the morphology of the molded bodies made from the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 11 was observed, the phase containing component (a) formed a continuous phase in all cases.

In Table 1, "CP" indicates that the phase containing component (a) forms a continuous phase.

In Table 2, "CP" indicates that the phase containing component (a) forms a continuous phase.

All of Examples 1 to 6 had excellent oil resistance and flame retardancy, and the resin composition according to this embodiment was able to produce molded articles that had both high oil resistance and flame retardancy.

The resin composition of the present invention can be used for molded articles that require high levels of oil resistance and flame retardancy.

Claims (6)

(a) (a-1) a polyphenylene ether-based resin or a mixed resin of (a-1) a polyphenylene ether-based resin and (a-2) a styrene-based resin;
(b) a hydrogenated block copolymer; and
(c) a phosphate ester compound; and
(d) a polyolefin resin; and
Including,
Relative to a total of 100 parts by mass of the component (a) and the component (b),
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 component (a) is the mixed resin, the amount of the polyphenylene ether resin (a-1) is 55 to 99.95 parts by mass per 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 a phase containing the component (a) forms a continuous phase. The resin composition according to claim 1, in which the amount of the (c) component is 10 to 20 parts by mass per 100 parts by mass of the total of the (a) component and the (b) component. The resin composition according to claim 1 or 2, in which the amount of the (d) component is 2 to 8 parts by mass per 100 parts by mass of the total of the (a) component and the (b) component. 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):
(In general formula (I), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, R11 and R12 independently represent a methyl group, and R13 and R14 independently represent a hydrogen atom or a methyl group.
In formula (II), Q1, Q2, Q3, and Q4 independently represent an alkyl group having 1 to 6 carbon atoms, and R11 and R12 each 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. A connection structure for a photovoltaic power generation module, comprising a molded body of the resin composition according to any one of claims 1 to 4. A junction box for a photovoltaic power generation module comprising a molded body of the resin composition according to any one of claims 1 to 4.