JP2022106668A - Resin composition, connection structure for solar power generation module, and junction box for solar power generation module - Google Patents

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

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.

Conventionally, polyphenylene ether-based resins have heat resistance, hydrolysis resistance, and flame retardancy in addition to excellent electrical insulation, so they are electrical and electronic components used in secondary batteries, photovoltaic power generation, etc. , Widely used in home appliances and OA equipment.

On the other hand, the polyphenylene ether-based resin composition does not have sufficient oil resistance, and cracks or cracks occur due to contact with rust preventives adhering to the mold of the molding machine, lubricating oil of various application parts, and the like. Sometimes it is a problem.

To solve such a problem, for example, Patent Document 1 states that in a resin composition composed of a polypropylene-based resin and a polyphenylene ether-based resin, the continuous phase is a polypropylene-based resin, which is excellent in heat resistance and flame retardancy. It is described that a sex resin composition can be obtained.

Japanese Unexamined Patent Publication No. 2000-344974

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

Therefore, an object of the present invention is to provide a resin composition having both high oil resistance and flame retardancy.

As a result of diligent studies to solve the above problems, (a) a polyphenylene ether-based resin or a mixed resin of a polyphenylene ether-based resin and a styrene-based resin, (b) a hydrogenated block copolymer, and (c) phosphorus. In a resin composition containing an acid ester-based compound and a predetermined melt flow rate (d) polyolefin-based resin, the content of each component is set within a specific range, and the phase containing the component (a) forms a continuous phase. As a result, it has been found that the above-mentioned problems can be solved advantageously, and the present invention has been completed.

（一般式（Ｉ）中、Ｑ１、Ｑ２、Ｑ３、及びＱ４は、独立に炭素数１～６のアルキル基を表し、Ｒ１１及びＲ１２は、メチル基を表し、Ｒ１３及びＲ１４は、独立に水素原子又はメチル基を表す。
一般式（ＩＩ）中、Ｑ１、Ｑ２、Ｑ３、及びＱ４は、独立に炭素数１～６のアルキル基を表し、Ｒ１１及びＲ１２は、メチル基を表す。
ｙは１以上の整数であり、ｎ１及びｎ２は、独立に０～２の整数を示し、ｍ１、ｍ２、ｍ３、及びｍ４は、独立に０～３の整数を示す。）
第５態様：第１～４態様のいずれか一つに記載の樹脂組成物の成形体を含む、太陽光発電モジュール用接続構造体。
第６態様：第１～４態様のいずれか一つに記載の樹脂組成物の成形体を含む、太陽光発電モジュール用ジャンクションボックス。 That is, the present invention is as follows.
First aspect: (a) (a-1) polyphenylene ether-based resin, or (a-1) a mixed resin of a polyphenylene ether-based resin and (a-2) styrene-based resin, and
(B) Hydrogenated block copolymer and
(C) Phosphate ester compounds and
(D) Polyolefin-based resin and
Including
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, and the amount 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, and the amount is 1 to 10 parts by mass.
When the component (a) is the mixed resin, the amount of the polyphenylene ether-based resin (a-1) 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 minutes or more.
A resin composition in which the phase containing the component (a) forms a continuous phase.
Second aspect: The resin composition according to the first aspect, 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).
Third aspect: 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). thing.
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 the 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 represents a methyl group.
In the 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. )
Fifth aspect: A connection structure for a photovoltaic power generation module, which comprises 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, which comprises a molded body of the resin composition according to any one of the first to fourth aspects.

According to the present invention, it is possible to obtain a resin composition having both high oil resistance and flame retardancy.

Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and carried out within the scope of the gist thereof.

In this embodiment, (a-1) polyphenylene ether-based resin, (a-2) styrene-based resin, (b) hydrogenated block copolymer, (c) phosphoric acid ester-based compound, and (d) polyolefin-based resin are used. They may be referred to as a component (a-1), a component (a-2), a component (b), a component (c), and a component (d), respectively. Further, in the present embodiment, the component (a-1) may be used alone, or the component (a-1) and the component (a-2) may be collectively referred to as the component (a).

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

In the present embodiment, the melt flow rate (hereinafter, may be referred to as “MFR”) refers to a value measured in accordance with JIS K7210. Unless otherwise specified in the present specification, JIS K7210 and the JIS standard of each resin, the measured load of 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. Further, for example, MFR (230 ° C., 2.16 kg) means 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 the melt flow rate according to the type of resin to be measured. For example, polypropylene is 230 ° C. and polyethylene is 190 ° C. When the component (d) is composed of a plurality of different polyolefin resins, the measurement temperature of the polyolefin resin is 50% or more of the total mass of the polyolefin resins.

-Resin composition The resin composition of the present embodiment is
(A) (a-1) Polyphenylene ether-based resin, or (a-1) Polyphenylene ether-based resin and (a-2) Styrene-based resin mixed resin,
(B) Hydrogenated block copolymer and
(C) Phosphate ester compounds and
(D) Polyolefin-based resin and
Including
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, and the amount 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, and the amount is 1 to 10 parts by mass.
When the component (a) is the mixed resin, the amount of the polyphenylene ether-based resin (a-1) 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 minutes or more.
It is a resin composition in which the phase containing the component (a) forms a continuous phase.

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

The component (a) may be only one kind or a combination of two or more kinds.

一般式（ＩＩＩ）中、Ｏは、酸素原子であり、Ｒ２１～Ｒ２４は、独立して、水素原子、ハロゲン原子、第一級又は第二級の炭素数１～８のアルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基、及びハロ炭化水素オキシ基（但し、少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てている。）からなる群より選ばれるいずれかを表わす。 -Component (a-1) The component (a-1) contained in the resin composition of the present embodiment includes a copolymer composed of the following structural units of the general formula (III) and structural units of the general formula (III). Any of the copolymers having (hereinafter, may be simply referred to as "polyphenylene ether") can be used.

In the general formula (III), O is an oxygen atom, and R21 to R24 are independently hydrogen atoms, halogen atoms, primary or secondary alkyl groups having 1 to 8 carbon atoms, and phenyl groups. Represents any one selected from the group consisting of a haloalkyl group, an aminoalkyl group, a hydrocarbon oxy group, and a halohydrocarbon oxy group (where at least two carbon atoms separate the halogen atom and the oxygen atom). ..

The homopolymer of the polyphenylene ether-based resin is not limited to the following, but for example, poly (2,6-dimethyl-1,4-phenylene ether) and 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.

The polymer of the polyphenylene ether-based resin is not limited to the following, but is, for example, a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol). And a copolymer with 2-methyl-6-butylphenol).

Among these, as polyphenylene ether-based resins, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6- A copolymer with trimethylphenol or a mixture thereof is preferable.

The method for producing the polyphenylene ether-based resin used in the present embodiment is not limited to the following, and is, for example, US Pat. Nos. 3,306,874, 330,875, 325,357, and the same. Examples thereof include known production methods described in Japanese Patent Application Laid-Open No. 32573358, Japanese Patent Application Laid-Open No. 50-51197, Japanese Patent Application Laid-Open No. 52-17880, Japanese Patent Application Laid-Open No. 63-152628, and the like.

The reduced viscosity of the polyphenylene ether-based resin is preferably in the range of 0.30 to 0.65 dL / g from the viewpoint of molding fluidity and physical property balance. It is more preferably in the range of 0.40 to 0.60 dL / g, and even more preferably in the range of 0.45 to 0.55 dL / g. When the reduced viscosity is 0.30 dL / g or more, the impact resistance or the oil resistance is excellent. Further, when the reducing viscosity is 0.65 dL / g or less, the molding fluidity is excellent. In the present embodiment, the reduced viscosity of the polyphenylene ether-based resin is a value measured with a 0.5 g / dL chloroform solution at 30 ° C. and an Ubbelohde type viscosity tube.

In the present embodiment, a mixture of two or more kinds of polyphenylene ether-based resins having different reducing viscosities can also be preferably used.

In addition, the (a-1) polyphenylene ether-based resin of the present embodiment may contain modified polyphenylene ether in which all or part of it is modified. The modified polyphenylene ether referred to here has at least one carbon-carbon double bond or triple bond in the molecule, and is composed of a group consisting of a carboxylic acid group, an acid anhydride group, an amino group, a hydroxy group and a glycidyl group. It refers to a polyphenylene ether modified with a modified compound having at least one selected 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.

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) 100 ° C. or higher and lower than the glass transition temperature of the polyphenylene ether. A method of reacting with a modified compound at temperature, (2) a method of melt-kneading and reacting with a modified compound at a temperature in the range of the glass transition temperature of polyphenylene ether or more and 360 ° C. or less, (3) at a temperature lower than the glass transition temperature of polyphenylene ether. , A method of reacting the polyphenylene ether with the modified compound in a solution and the like. From the viewpoint of productivity, the method (1) or (2) is preferable.

Next, the modified compound used for producing the modified polyphenylene ether will be described.

The modified compound having a carbon-carbon double bond in the molecule and having a carboxylic acid group or an acid anhydride group at the same time is not limited to the following, but is not limited to, for example, maleic acid, fumaric acid, and chloromaleic acid. , Unsaturated dicarboxylic acids such as cis-4-cyclohexene-1,2-dicarboxylic acid, and acid anhydrides thereof. In particular, fumaric acid, maleic acid, and maleic anhydride are preferable, and fumaric acid and maleic anhydride are more preferable, from the viewpoint of reactivity with the polyphenylene ether-based resin.

Further, a compound in which one or two of the two carboxyl groups of the unsaturated dicarboxylic acid is an ester can also be used as a modified compound.

The modified compound having a carbon-carbon double bond in the molecule and having a glycidyl group at the same time is not limited to the following, and is, for example, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and epoxidized natural fats and oils. And so on. Of these, glycidyl acrylate and glycidyl methacrylate are preferable.

The modified compound having a carbon-carbon double bond in the molecule and having a hydroxy group at the same time is not limited to the following, and is, for example, allyl alcohol, 4-penten-1-ol, 1,4-. Unsaturated alcohols of the general formula C _n H _2n-1 OH, C _n H _2n-3 OH (where n is a positive integer), such as pentadiene-3-ol, general formula C _n H _2n-5 OH, Examples thereof include unsaturated alcohols such as C _n H _2n-7 OH (in the formula, 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 modified compound added when producing the modified polyphenylene ether is preferably 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, based on 100 parts by mass of the polyphenylene ether, for example, from the viewpoint of modification efficiency. More preferably, 0.5 to 3 parts by mass is further preferable.

When producing a modified polyphenylene ether using a radical initiator, the amount of the radical initiator added is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the polyphenylene ether from the viewpoint of the modification rate and the balance of physical properties, and is 0. 0.01 to 0.5 parts by mass is more preferable, and 0.05 to 0.3 parts by mass is further preferable.

The addition rate of the modified compound to the modified polyphenylene ether is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and 0.1 to 1% by mass with respect to 100% by mass of the modified polyphenylene ether. Mass% is more preferred.

The unreacted modified compound and the polymer of the modified compound may remain in the modified polyphenylene ether. The amount of the unreacted modified compound and the polymer of the modified compound remaining is preferably less than 5% by mass, more preferably 3% by mass or less, still more preferably 1% by mass or less.

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

The styrene-based compound is not limited to the following, but is, for example, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene. Etc., and among them, styrene is preferable.

The copolymerizable compound is not limited to the following, but for example, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacryl nitrile; acids such as maleic anhydride. Anhydrous and the like can be mentioned.

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.

Examples of the rubbery polymer include a conjugated diene-based rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, and an ethylene-propylene copolymer-based rubber. Among them, polybutadiene, styrene-butadiene random copolymer, styrene-butadiene block copolymer, and a rubber component obtained by partially or substantially completely or completely hydrogenating these (for example, a hydrogenation rate of 50 to 100). The rubber component (%) is preferable.

The component (a-2) is not limited to the following, but is, for example, homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile. Examples thereof include a copolymer (ABS resin) and other styrene-based copolymers. Among them, the component (a-2) is preferably one or more selected from the group consisting of homopolystyrene and rubber-modified polystyrene (HIPS) from the viewpoint of compatibility with the polyphenylene ether-based resin.

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

The (b) hydrogenated block copolymer of the present embodiment is a block copolymer of an aromatic vinyl compound (for example, styrene) and a conjugated diene compound, that is, a polystyrene block and a conjugated diene compound polymer block. It is a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of.

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

As for the structure of the block copolymer before hydrogenation, when the block copolymer is a block copolymer of styrene and a conjugated diene compound, the styrene block chain is represented as S and the diene compound block chain is represented as B. For example, SBS, SBS, (SB) ₄ -S, SBS, SBS, and the like can be mentioned.

Further, the microstructure of the polymer block of the conjugated diene compound (bonded form of the conjugated diene compound) can be arbitrarily selected. The vinyl bond amount of the conjugated diene compound polymer block (total of 1,2-vinyl bond and 3,4-vinyl bond) is the total bond amount of the conjugated diene compound polymer (1,2-vinyl bond and 3,4). -The total of the vinyl bond and the 1,4-conjugated bond) is preferably 2 to 60%, more preferably 8 to 40%.

The number average molecular weight of the 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 the component (b) is 100,000 or more, a resin composition having excellent impact resistance can be obtained. The impact resistance of the resin composition of the present embodiment is improved in proportion to the number average molecular weight of the component (b), and when the number average molecular weight of the component (b) is 400,000 or less, the resin composition at the time of melt extrusion A resin composition having a low load and excellent processing fluidity can be obtained, and the dispersibility of the component (b) in the resin composition is excellent.

When the component (b) has a styrene polymer block chain, it is preferable that at least one styrene polymer block chain has a number average molecular weight of 15,000 or more. More preferably, it is 20,000 to 50,000. More preferably, the number average molecular weight of all styrene polymer block chains is 15,000 or more.

When the component (b) has a styrene polymer block chain, the proportion of the styrene polymer block chain of the component (b) is particularly limited as long as the number average molecular weight of the styrene polymer block chain is in the above range. However, from the viewpoint of impact resistance, it is preferably 10 to 70% by mass, more preferably 20 to 50% by mass, and further preferably 30 to 40% by mass.

As the component (b), two or more hydrogenated block copolymers having different compositions or structures can be used in combination. For example, a combined use of a hydrogenated block copolymer having a bonded styrene polymer block content of 50% by mass or more and a hydrogenated block copolymer having a bonded styrene polymer block content of 30% by mass or less, or hydrogenation having different molecular weights. Combined use of block copolymers, a block copolymer containing a block copolymer of styrene and a conjugated diene compound as described above and a random copolymer block of styrene and a conjugated diene compound as described above are hydrogenated. Examples thereof include combined use with the obtained hydrogenated random block copolymer.

The "bonded styrene polymer block content" refers to the proportion of the styrene polymer block chain in the component (b).

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

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

The component (c) is not limited to the following, but is, for example, triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis [di (2,6-dimethylphenyl) phosphate], Examples thereof include 2,2-bis {4- [bis (phenoxy) phosphoryloxy] phenyl} propane and 2,2-bis {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane. Further, as the component (c), for example, a phosphate ester such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresylphenyl phosphate, octyldiphenyl phosphate, diisopropylphenyl phosphate and the like. Flame retardant; Diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzylphosphonate, dimethyl-4-hydroxy-3,5-dibromobenzylphosphonate, diphenyl-4-hydroxy-3,5 -Dibromobenzyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3) -Monophosphate ester compounds such as dibromopropyl) phosphate, bis (chloropropyl) monooctyl phosphate, hydroquinonyldiphenyl phosphate, phenylnonylphenylhydroquinonyl phosphate, phenyldinonylphenyl phosphate; and aromatic condensed phosphate ester compounds, etc. Can be mentioned. Among these, aromatic condensed phosphoric acid ester compounds are preferable because they generate less gas during processing and are excellent in thermal stability and the like.

The aromatic condensed phosphoric acid ester compound is commercially available and is not limited to the following, but for example, the trade names "CR741", "CR733S", "PX200", "E890" of Daihachi Chemical Industry Co., Ltd. , "FP600", "FP700", "FP800" and the like, which are trade names of ADEKA CORPORATION.

一般式（Ｉ）中、Ｑ１、Ｑ２、Ｑ３、及びＱ４は、独立に炭素数１～６のアルキル基を表し、Ｒ１１及びＲ１２は、メチル基を表し、Ｒ１３及びＲ１４は、独立に水素原子又はメチル基を表す。一般式（ＩＩ）中、Ｑ１、Ｑ２、Ｑ３、及びＱ４は、独立に炭素数１～６のアルキル基を表し、Ｒ１１及びＲ１２は、メチル基を表す。ｙは１以上の整数であり、ｎ１及びｎ２は、独立に０～２の整数を示し、ｍ１、ｍ２、ｍ３、及びｍ４は、独立に０～３の整数を示す。 As the component (c) used in the present embodiment, the aromatic condensed phosphoric acid ester represented by the following general formula (I) or the following general formula (II) is preferable, and the aromatic condensed phosphoric acid represented by the general formula (I) is preferable. Esters are more preferred.

In the 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 hydrogen atom. Represents a methyl group. In the 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.

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

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

The component (c) preferably contains the aromatic condensed phosphoric acid ester of the formula (I) in an amount of 50 to 100% by mass with respect to 100% by mass of the component (c).

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

The component (c) preferably contains the aromatic condensed phosphoric acid ester of the formula (II) in an amount of 50 to 100% by mass with respect to 100% by mass of the component (c).

It is more preferable that the aromatic condensed phosphoric acid 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 a monomer unit containing olefins (for example, α-olefins). Examples of the component (d) include homopolymers of ethylene, propylene and other olefin hydrocarbons, and copolymers thereof. (D) The component may be only one kind or a combination of two or more kinds. Examples of the component (d) include polyethylene such as low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polybutene and the like. Examples of the preferable component (d) include polyethylene and polypropylene from the viewpoint of oil resistance and impact resistance.

The melt flow rate of the component (d) is 30 g / 10 minutes or more, preferably 40 g / 10 minutes or more, and more preferably 50 g / 10 minutes or more. The MFR of the component (d) is preferably 200 g / 10 minutes or less, more preferably 150 g / 10 minutes or less, and more preferably 100 g / 10 minutes or less. By setting the MFR of the component (d) to 30 g / 10 minutes or more, the polyolefin-based resin is likely to be present on the surface portion (for example, within 2 μm from the surface) of the molded product of the resin composition, and the oil resistance is excellent.

(D) When the component 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 polyethylene MFR (190 ° C., 2.16 kg) is 30 g / 10 min or more, 40 g / 10 min or more, 50 g / 10 min or more. In another embodiment, the polyethylene MFR (190 ° C., 2.16 kg) 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 minutes or more, the polyolefin resin is likely to be present on the surface portion (for example, within 2 μm from the surface) of the molded product of the resin composition. In particular, when the MFR (190 ° C., 2.16 kg) of polyethylene is 100 g / 10 minutes or less, the flame retardancy of the resin composition tends to be remarkably improved.

(D) When the component is polyproprene, 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 polypropylene MFR (230 ° C., 2.16 kg) is 30 g / 10 min or more, 40 g / 10 min or more, 50 g / 10 min or more. In another embodiment, the polypropylene MFR (230 ° C., 2.16 kg) 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 minutes or more, the polyolefin-based resin is likely to be present on the surface portion (for example, within 2 μm from the surface) of the molded product of the resin composition.

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

-Other Flame Retardants Various conventionally known flame retardants and flame retardant aids may be added to the resin composition of the present embodiment. Examples of other flame retardants include alkaline earth metal hydroxides such as phosphinate and magnesium hydroxide, aluminum hydroxide, alkali metal hydroxides, zinc borate compounds, and zinc nitrate compounds.

-Additives In order to impart other properties to the resin composition of the present embodiment, for example, other than the components (a), (b) and (d), as long as the effects of the present invention are not impaired. Additives such as resins, plasticizers, antioxidants, stabilizers such as UV absorbers, antistatic agents, mold release agents, dyes, pigments, fillers, reinforcing materials, spreading agents and the like can be added.

-Content of each component In the resin composition of the present embodiment, the amount of the components (a) to (d) is the amount of the component (a) with respect to the total of 100 parts by mass of the components (a) and (b). The amount is 60 to 90 parts by mass, the amount of (b) component is 10 to 40 parts by mass, the amount of (c) component is 8 to 25 parts by mass, and the amount of (d) component is 1 to 10 parts. It is a mass part.

In the resin composition of the present embodiment, the contents of the component (a) and the component (b) are based on 100 parts by mass of the total of the component (a) and the component (b) from the viewpoint of flame retardancy and oil resistance. , Preferably (a) component: 65 to 90 parts by mass, (b) component: 10 to 35 parts by mass, and more preferably (a) component: 65 parts by mass to 85 parts by mass, (b) component: 15 parts by mass. It is parts to 35 parts by mass, more preferably (a) component: 70 parts by mass to 85 parts by mass, and (b) component: 15 parts by mass to 30 parts by mass. Specifically, when the amount of the component (a) is 60 parts by mass or more, the flame retardancy and rigidity are excellent, and when the amount of the component (b) is 10 parts by mass or more, the oil resistance and the impact resistance tend to be excellent. It is in.

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

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

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

The content of the component (d) is 1 to 10 parts by mass with respect to 100 parts by mass in total of the components (a) and (b) from the viewpoint of flame retardancy and oil resistance. It is preferably 2 to 8 parts by mass, and more preferably 3 to 7 parts by mass. (D) When the amount of the polyolefin resin is 1 part by mass or more, the oil resistance tends to be excellent, and when the amount 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 shall be 40 parts by mass or less with respect to 100 parts by mass in total of the components (a) and (b) from the viewpoint of fluidity and appearance. Is more preferable, and it is more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less. When the content of the other flame retardant 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, still more preferably 3% by mass or less, based on 100% by mass in the resin composition.

-Morphology As the morphology of the resin composition of the present embodiment, from the viewpoint of flame retardancy, the phase containing the component (a) forms a continuous phase. This morphology is 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. can do.

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

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

In the method for producing the resin composition of the present embodiment, the melt-kneading temperature and the screw rotation speed can be appropriately selected from the range of the melt-kneading temperature of 100 to 370 ° C. and the screw rotation speed of 100 to 1200 rpm.

Examples of the raw material supply device for supplying the raw material to the twin-screw extruder include a loss-in weight feeder, a single screw feeder, a twin-screw screw feeder, a table feeder, a rotary feeder, and the like. A loss-in weight feeder is preferable from the viewpoint of less.

(Molded body)
By molding the resin composition of the present embodiment, a molded product can be obtained. The molded product contains at least the resin composition of the present embodiment.

As the molding method, for example, known molding methods such as injection molding, hollow molding, extrusion molding, sheet molding, film molding and the like can be used, and injection molding is particularly preferable. Examples of the injection molding machine include the trade name "SH100C" manufactured by Sumitomo Heavy Industries, Ltd.

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

The molded body can be used as various molded bodies, and can be used in a wide range of fields such as industrial parts, electrical / electronic parts, office equipment housings, automobile parts, precision parts, etc., in particular, module connectors for photovoltaic power generation and solar cells. It can be suitably used for a connection structure for a photovoltaic power generation module such as a junction box for solar power generation.

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

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

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

The raw materials used for the resin compositions of Examples and Comparative Examples are shown below.
-Component (a) Component (a-1): Poly (2,6-dimethyl-1,4-phenylene ether) having a reducing viscosity of 0.5 dL / g.
(A-2) Ingredients: rubber-modified polystyrene (HIPS), manufactured by Petrochemical, trade name "CT60", content of rubbery polymer: 10% by mass

(B) Ingredients Made by TSRC, trade name "TAIPOL6151", number average molecular weight: about 280,000

-(C) component (c-1) component: manufactured by Daihachi Chemical Industry Co., Ltd., trade name "E890", aromatic condensed phosphoric acid ester compound

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

Other flame retardants: Made by Clariant, trade name "Exolit® OP 930"

Other materials used in the examples are shown below.
Processing oil: Made by Nihon Kohsakuyu, trade name "G-6280"

The apparatus used in the examples is 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: KEYENCE, product name "VHX-5000"
Transmission electron microscope (TEM): Hitachi High-Technologies Corporation, product name "HT7700"

(Examples 1 to 6, Comparative Examples 1 to 11)
The components (a) to (d) and other flame retardants are supplied to the twin-screw extruder with the compositions shown in Tables 1 and 2, and the extrusion temperature is 300 to 320 ° C., the screw rotation speed is 300 rpm, and the discharge rate is 15 kg / hour. The resin composition was melt-kneaded under the above conditions to obtain pellets of the resin composition. The settings of the twin-screw extruder are as follows: The number of barrels is 12 blocks, and the upstream supply port is provided in the 1st barrel from the upstream and the liquid addition pump is provided in the 7th barrel in the flow direction of the raw material. A vacuum vent was provided at the 11th barrel.

The method of measuring the physical properties in Examples and Comparative Examples is shown below.

The oil-resistant resin composition pellets were supplied to a small injection molding machine set to a cylinder temperature of 280 ° C., and a flat plate of 120 mm × 80 mm × 3 mm was formed 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 having a longitudinal direction perpendicular to the flow direction was cut out. This test piece is placed on the curved surface of a parabolic bending bar whose vertical cross section is represented by the equation y2 ⁼ 6x (x ≧ 0, y ≧ 0) with the horizontal direction as the x-axis and the vertical direction as the y-axis. , It was attached using a jig so that there was no gap between the bar and the test piece. Further, the bending bar has the position where x = 0 and y = 0 on the vertical cross section as the arrangement position of the measurement starting point side end of the test piece, and the position where x> 0 and y> 0 is the measurement of the test piece. It is the placement position of the end side.

Next, processing oil was applied to the surface of the test piece and left at 40 ° C. for 24 hours. After 24 hours, when a crack occurred on the surface of the test piece, the critical position where the crack occurred (the position where the value of x became the largest in the x-axis direction of the bending bar) was read.

To read the critical position where cracks occur, transfer the scale of the x-axis coordinates of the bending bar to the test piece while it is attached to the bending bar, remove the test piece from the bending bar, and then confirm the presence of cracks. , The position where the crack exists was read in comparison with the posted scale (the critical position is the position corresponding to the x-axis coordinate of the bending bar, so it is not the periphery length of the test piece). In the present disclosure, the crack is a crack in the flow direction of 200 μm or more, which is observed when the surface of the test piece is observed using a microscope.

Then, the critical strain (%) was calculated from the thickness of the test piece and the critical position where cracks were generated by the following equation. The critical strains of each Example and Comparative Examples were indexed with the critical strain (%) of Comparative Example 1 as 100. It was judged that the larger the index value, the better the oil resistance.
Critical strain (%) = d × 3 ^{1/2/2 (3 + 2x) 3/2 ×} 100
d: Specimen thickness (inch)
x: Critical position where cracks occur (inch)

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

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

A gas burner flame was applied to the test piece, and the degree of combustion was evaluated. In addition, the flame retardancy class was shown as the flame retardancy class classified by the UL94 vertical test. Five tests were performed on all the test pieces to make a judgment. The outline of the classification method is as follows.
Flame retardancy evaluation criteria V-0 (pass): Total burning time of 5 pieces is 50 seconds or less, maximum burning time is 10 seconds or less, and no flame dripping is satisfied. Vоut: Total burning time of 5 pieces is more than 250 seconds, Satisfy any one or more of maximum burning time over 30 seconds and with flame dripping

-Morphology From the molded product prepared in the same manner as the test piece for oil resistance evaluation, an ultrathin section having a thickness of several tens to 100 nm was prepared using an ultramicrotome. Then, it was stained with osmium tetroxide and ruthenium tetroxide, and the ultrathin section after staining was observed with a transmission electron microscope to obtain an image at a magnification of 10,000 times. From the obtained image, it was determined whether or not the phase containing the component (a) formed a continuous phase.

When the morphology of the molded product prepared from the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 11 was observed, the phase containing the component (a) formed a continuous phase in each case.

表１中、「ＣＰ」は、（ａ）成分を含有する相が連続相を形成していることを示す。

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

表２中、「ＣＰ」は、（ａ）成分を含有する相が連続相を形成していることを示す。

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

All of Examples 1 to 6 are excellent in oil resistance and flame retardancy, and the resin composition according to the present embodiment could form a molded product having both high oil resistance and flame retardancy.

The resin composition of the present invention can be used for a molded product that requires a high degree of oil resistance and flame retardancy.

Claims (6)

(A) (a-1) Polyphenylene ether-based resin, or (a-1) Polyphenylene ether-based resin and (a-2) Styrene-based resin mixed resin,
(B) Hydrogenated block copolymer and
(C) Phosphate ester compounds and
(D) Polyolefin-based resin and
Including
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, and the amount 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, and the amount is 1 to 10 parts by mass.
When the component (a) is the mixed resin, the amount of the polyphenylene ether-based resin (a-1) 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 minutes or more.
A resin composition in which the phase containing the component (a) forms a continuous phase. 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). 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). The resin composition according to any one of claims 1 to 3, wherein the component (c) is a phosphoric acid ester compound represented by the following general formula (I) or general formula (II).

(In the 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 represents a methyl group.
In the 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. ) A connection structure for a photovoltaic power generation module, which comprises 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, which comprises a molded body of the resin composition according to any one of claims 1 to 4.