WO2020004440A1

WO2020004440A1 - Polyimide resin composition and molded body of same

Info

Publication number: WO2020004440A1
Application number: PCT/JP2019/025308
Authority: WO
Inventors: 篤上福
Original assignee: 大塚化学株式会社
Priority date: 2018-06-27
Filing date: 2019-06-26
Publication date: 2020-01-02
Also published as: JPWO2020004440A1; TW202006043A

Abstract

Provided are the following: a phosphazene compound-containing polyimide resin composition which exhibits excellent molding processing properties and high thermal stability and does not undergo bleeding out; and a molded body of same. The polyimide resin composition contains a thermoplastic polyimide resin (A) and a phosphazene compound (B), and the phosphazene compound (B) is a compound represented by formula (5).

Description

Polyimide resin composition and molded product thereof

The present invention relates to a polyimide resin composition and a molded product thereof.

Polyimide resins are used in a wide range of fields because they have high heat resistance, high strength, and high solvent resistance due to rigidity of molecular chains, resonance stabilization, and strong chemical bonding. In addition, since a polyimide resin having crystallinity can further improve its heat resistance, strength, and chemical resistance, it is expected to be used as a metal substitute material. However, while the conventional polyimide resin has high heat resistance, it does not have a melting point at a temperature lower than the decomposition temperature and does not exhibit thermoplasticity.

In recent years, polyimide resins having thermoplasticity have been reported. Thermoplastic polyimide resin has excellent moldability in addition to the inherent heat resistance of the polyimide resin, so harsh environments that could not be applied with conventional thermoplastic resins such as polyamide resin or polyphenylene sulfide resin Application to moldings used below is also possible. Aurum (registered trademark) and the like are known as thermoplastic polyimide resins. Although this resin has a plurality of flexible ether bonds and meta structures in the structure, it is a rigid wholly aromatic polyimide, but has a melting point below the decomposition temperature, but since its melting point is still high, In molding, a high temperature exceeding 400 ° C. is required, and there is a problem in equipment restrictions and handling properties.

Therefore, a thermoplastic polyimide resin which is easy to mold and has excellent heat resistance has been proposed (for example, Patent Document 1). Patent Document 1 describes that a thermoplastic polyimide resin having excellent heat resistance can be obtained by introducing an aliphatic structure into a polymer main chain. However, the polyimide resin described in Patent Literature 1 has a problem that high flame retardancy, unlike the wholly aromatic polyimide resin, is not exhibited.

(4) As a method of making a thermoplastic resin flame-retardant, a method of adding a flame retardant such as a chlorine compound, a bromine compound, or antimony trioxide to the thermoplastic resin is used. However, these are said to be unfavorable from the viewpoint of environmental protection, toxicity, and the like, and therefore, there is a need for an improved flame-retardant method.

Therefore, it has been studied to use a phosphorus-based flame retardant as an alternative flame retardant that does not contain halogens such as chlorine and bromine, and metal oxides. Conventionally, red phosphorus, phosphate esters, condensed phosphate esters, and the like have been used as phosphorus-based flame retardants. However, red phosphorus has problems such as hydrolysis and mold corrosion due to generation of corrosive phosphoric acid. Phosphate esters and condensed phosphate esters have relatively low phosphorus contents and poor hydrolysis resistance. On the other hand, phosphazene compounds have attracted attention because of their high phosphorus content and relatively good heat resistance and hydrolysis resistance. Patent Document 1 also discloses a phosphazene-based compound as a flame retardant that can be added to a thermoplastic polyimide resin.

On the other hand, when a large amount of the phosphazene-based compound is added to the thermoplastic resin, the phosphazene-based compound is easily eluted (bleed-out) on the surface of the molded body when the obtained molded body is exposed to a high temperature, and the flame-retardant performance is reduced. There is a possibility that a decrease, a decrease in adhesion to another molded body or a material, or the like may occur. In particular, as a resin used in a severe environment such as a thermoplastic polyimide resin, a phosphazene-based compound-containing resin composition having high thermal stability (heat resistance) and not causing bleed-out even when exposed to high temperatures Is required.

WO 2015/020020 pamphlet

The present invention has been made in view of the above circumstances, and provides a phosphazene-based compound-containing polyimide resin composition having excellent moldability, high thermal stability, and no bleed-out, and a molded article thereof. As an issue.

As a result of intensive studies, the present inventor has found that the above problem can be solved by adding a phosphazene-based compound having a specific structure to a thermoplastic polyimide resin, and has completed the present invention.

That is, the present invention provides the following polyimide resin composition and a molded article thereof.

{Item 1} A polyimide resin composition containing a thermoplastic polyimide resin (A) and a phosphazene-based compound (B), wherein the phosphazene-based compound (B) is a compound represented by the following formula (5).

Item 2. The polyimide resin composition according to item 1, wherein the thermoplastic polyimide resin (A) is a polymer having one or more structural units represented by the following general formulas (1) to (3). .

(Wherein, R ₁ is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure. X ₁ is a 4-6 group containing 6 to 30 carbon atoms containing at least one aromatic ring. Is a valence group.)

(In the formula, R ₂ is a divalent chain aliphatic group having 5 to 20 carbon atoms. X ₂ is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.)

(Wherein, R ₃ is a divalent group having 6 to 22 carbon atoms containing at least one aromatic ring. X ₃ is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring. is there.)

Item 3. The item in Item 2, wherein the total content ratio of the structural units represented by the general formulas (1) to (3) to all structural units constituting the thermoplastic polyimide resin (A) is 50 to 100 mol%. Polyimide resin composition.

{Item 4} The polyimide resin composition according to any one of Items 1 to 3, wherein the thermoplastic polyimide resin (A) has a glass transition temperature of 170 ° C. or higher.

{Item 5} The polyimide resin composition according to any one of Items 1 to 4, wherein the melting point of the thermoplastic polyimide resin (A) is 390 ° C. or less.

Item 6: The polyimide resin composition according to any one of Items 1 to 5, wherein the content of the thermoplastic polyimide resin (A) is 50 to 99% by mass based on 100% by mass of the total amount of the polyimide resin composition. object.

Item 7: The polyimide resin composition according to any one of Items 1 to 6, wherein the content of the phosphazene compound (B) is 1 to 50% by mass based on 100% by mass of the total amount of the polyimide resin composition. .

{Item 8} A molded article produced using the polyimide resin composition according to any one of Items 1 to 7.

{Item 9} The molded article according to item 8, which is in the form of a film.

{Item 10} A method for producing a molded article, comprising a step of thermoforming the polyimide resin composition according to any one of Items 1 to 7 at 300 to 400 ° C.

Since the polyimide resin composition of the present invention has a compound represented by the formula (5) as a flame retardant, it has excellent moldability and high thermal stability (heat resistance). When a molded article is produced, elution of the compound to the surface can be suppressed even when exposed to high temperatures.

Hereinafter, an example of a preferred embodiment of the present invention will be described. However, the following embodiments are merely examples. The present invention is not limited to the following embodiments.

<Polyimide resin composition>
The polyimide resin composition of the present invention is characterized by containing a thermoplastic polyimide resin (A) and a phosphazene-based compound (B), and may further contain other additives as necessary.

各 Each component of the polyimide resin composition of the present invention will be described below.

(Thermoplastic polyimide resin (A))
Thermoplastic polyimide resin (A) (hereinafter sometimes abbreviated as “resin (A)”) is a resin that can be melt-molded by heating, and is a polymer having an imide ring structure in a repeating unit (structural unit) ( Any known polymer (polymer) can be widely used. Examples of the resin (A) include polymers having one or more structural units represented by general formulas (1) to (3).

The total content of the structural units represented by the general formulas (1) to (3) with respect to all the structural units constituting the resin (A) is usually 50 to 100 mol%, preferably 75 to 100 mol%. %, More preferably 80 to 100 mol%, still more preferably 85 to 100 mol%, and particularly preferably 95 to 100 mol%.

Examples of the structural unit that the resin (A) can contain in addition to the structural units represented by the general formulas (1) to (3) include, for example, a structural unit represented by a general formula (4) described later. Can be mentioned.

As the resin (A), a polymer having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), or a structural unit represented by the general formula (1), It is preferable that the polymer has a structural unit represented by the formula (2) and a structural unit represented by the general formula (3).

When the resin (A) is a polymer having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), the structural unit represented by the general formula (1) and the general formula The content ratio of the structural unit represented by the general formula (1) to the total amount of the structural unit represented by the formula (2) is preferably from 40 to 70 mol%, more preferably from 40 to 60 mol%. By setting the content ratio to the above range, the half-crystallization time of the polyimide resin is 60 seconds or less, and since the crystallization speed is high, it is possible to sufficiently crystallize the polyimide resin even in a general injection molding cycle. Become.

When the resin (A) is a polymer having a structural unit represented by the general formula (1), a structural unit represented by the general formula (2) and a structural unit represented by the general formula (3), The content ratio of the structural unit represented by the general formula (1) to the total of the structural unit represented by the general formula (2) and the structural unit represented by the general formula (2) is preferably 40 to 70 mol%. , More preferably 40 to 60 mol%. By setting the content ratio to the above range, the half-crystallization time of the polyimide resin is 60 seconds or less, and since the crystallization speed is high, it is possible to sufficiently crystallize the polyimide resin even in a general injection molding cycle. Become. Further, the content ratio of the structural unit represented by the general formula (3) to the total of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is preferably 25 mol%. From the viewpoint of maintaining the crystallinity, it is more preferably at most 20 mol%, further preferably at most 15 mol%. On the other hand, the lower limit is not particularly limited and may be more than 0 mol%, and is preferably 5 mol% or more, more preferably 10 mol% or more from the viewpoint of improving heat resistance.

構造 Hereinafter, the structural unit represented by the general formula (1) will be described in detail.

R ₁ is a divalent group having 6 to 22 (preferably 8 to 17) carbon atoms containing at least one alicyclic hydrocarbon structure. Here, the alicyclic hydrocarbon structure means a ring derived from an alicyclic hydrocarbon compound. The alicyclic hydrocarbon compound may be saturated or unsaturated, and may be monocyclic or polycyclic.

Examples of the alicyclic hydrocarbon structure include a cycloalkane ring such as a cyclohexane ring; a cycloalkene ring such as cyclohexene; a bicycloalkane ring such as a norbornane ring; a bicycloalkene ring such as norbornene; Among these, a cycloalkane ring is preferred, a cycloalkane ring having 4 to 7 carbon atoms is more preferred, and a cyclohexane ring is still more preferred.

R ₁ contains at least one, preferably 1 to 3 alicyclic hydrocarbon structures.

R ₁ is preferably a divalent group represented by formula (R1-1) or (R1-2).

(In the formula, m ₁₁ and m ₁₂ are each independently an integer of 0 to 2, preferably 0 or 1. m ₁₃ to m ₁₅ are each independently an integer of 0 to 2, preferably Is 0 or 1.)

R ₁ is particularly preferably a divalent group represented by the general formula (R1-3). In the divalent group represented by the general formula (R1-3), the positional relationship between the two methylene groups with respect to the cyclohexane ring may be cis or trans, and the ratio of cis to trans is not limited. It may be a value.

X ₁ is a tetravalent group having 6 to 22 carbon atoms (preferably having 6 to 18 carbon atoms) containing at least one aromatic ring. The aromatic ring may be a single ring or a condensed ring. Examples of the aromatic ring include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.

X ₁ contains at least one aromatic ring, and preferably contains 1 to 3 aromatic rings.

X ₁ is preferably a tetravalent group represented by any of formulas (X1-1) to (X1-4).

(In the formula, R ₁₁ to R ₁₈ are each independently an alkyl group having 1 to 4 carbon atoms. P ₁₁ to p ₁₃ are each independently an integer of 0 to 2, preferably 0. P ₁₄ to p ₁₆ and p ₁₈ are each independently an integer of 0 to 3, and preferably 0. p ₁₇ is an integer of 0 to 4, preferably 0. L ₁₁ to L ₁₃ are each independently a single bond, an ether group, a carbonyl group or an alkylene group having 1 to 4 carbon atoms.)

Since X ₁ is a tetravalent group having at least one aromatic ring and having 6 to 22 carbon atoms, R ₁₂ , R ₁₃ , p ₁₂ and p ₁₃ in the general formula (X1-2) are represented by the general formula The carbon number of the tetravalent group represented by (X1-2) is selected so as to fall within the range of 6 to 22. Similarly, L ₁₁ , R ₁₄ , R ₁₅ , p ₁₄ and p ₁₅ in the general formula (X1-3) represent a tetravalent group represented by the general formula (X1-3) having 6 to 22 carbon atoms. L ₁₂ , L ₁₃ , R ₁₆ to R ₁₈ and p ₁₆ to p ₁₈ in the general formula (X1-4) are selected to be within the range, and are tetravalent groups represented by the general formula (X1-4) Is selected so that the number of carbon atoms is in the range of 6 to 22.

X ₁ is particularly preferably a tetravalent group represented by formula (X1-5) or (X1-6).

構造 Hereinafter, the structural unit represented by the general formula (2) will be described in detail.

R ₂ is a divalent chain aliphatic group having 5 to 20 carbon atoms (preferably 5 to 16 carbon atoms, more preferably 5 to 12 carbon atoms). Here, the chain aliphatic group means a group derived from a chain aliphatic compound. The chain aliphatic compound may be saturated or unsaturated, linear or branched, and may contain a hetero atom such as an oxygen atom.

R ₂ is preferably an alkylene group having 5 to 20 carbon atoms, more preferably an alkylene group having 5 to 16 carbon atoms, further preferably an alkylene group having 5 to 12 carbon atoms, and particularly preferably an alkylene group having 5 to 12 carbon atoms. It is an alkylene group of the number 6 to 10. The alkylene group may be a linear alkylene group or a branched alkylene group, and is preferably a linear alkylene group.

R ₂ is particularly preferably a hexamethylene group.

Another preferred embodiment of R _{2 is} a divalent linear aliphatic group having 5 to 20 carbon atoms (preferably 5 to 16 carbon atoms, more preferably 5 to 12 carbon atoms) including an ether group. Can be Among them, a divalent group represented by formula (R2-1) or (R2-2) is preferable.

(Wherein, m ₂₁ and m ₂₂ are each independently an integer of 1 to 19, preferably an integer of 1 to 15, more preferably an integer of 1 to 11, and further preferably 2 to 6 M ₂₃ to m ₂₅ are each independently an integer of 1 to 18, preferably an integer of 1 to 14, more preferably an integer of 1 to 10, and further preferably 2 to It is an integer of 4.)

Since R ₂ is a divalent chain aliphatic group having 5 to 20 carbon atoms (preferably 5 to 16 carbon atoms, more preferably 5 to 12 carbon atoms), R ₂ in the general formula (R2-1) m ₂₁ and m ₂₂ are such that the divalent group represented by the general formula (R2-1) has a carbon number of 5 to 20 (preferably 5 to 16 carbon atoms, more preferably 5 to 12 carbon atoms). Selected to enter. That is, m ₂₁ + m ₂₂ is 5 to 20 (preferably 5 to 16, more preferably 5 to 12). Similarly, m ₂₃ to m ₂₅ in the general formula (R2-2) are such that the divalent group represented by the general formula (R2-2) has 5 to 20 carbon atoms (preferably 5 to 16 carbon atoms). Preferably, the number of carbon atoms is selected to be in the range of 5 to 12). That is, m ₂₃ + m ₂₄ + m ₂₅ is 5 to 20 (preferably 5 to 16, and more preferably 5 to 12).

X ₂ is defined in the same manner as X ₁ in the general formula (1). Preferred aspects of X ₂ is the same as _{X 1.}

構造 Hereinafter, the structural unit represented by the general formula (3) will be described in detail.

R ₃ is a divalent group having 6 to 22 (preferably 6 to 18) carbon atoms containing at least one aromatic ring. The aromatic ring may be a single ring or a condensed ring. Examples of the aromatic ring include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.

R ₃ contains at least one aromatic ring, and preferably contains 1 to 3 aromatic rings.

Further, a monovalent or divalent electron withdrawing group may be bonded to the aromatic ring. Examples of the monovalent electron-withdrawing group include a nitro group, a cyano group, a p-toluenesulfonyl group, a halogen, a halogenated alkyl group, a phenyl group and an acyl group. Examples of the divalent electron-withdrawing group include a fluorinated alkylene group (eg, —C (CF ₃ ) ₂ —, — (CF ₂ ) _p — (where p is an integer of 1 to 10). Other than the halogenated alkylene group, there may be mentioned -C-, -SO _2- , -SO-, -CONH-, -COO- and the like.

R ₃ is preferably a divalent group represented by formula (R3-1) or (R3-2).

(Wherein m ₃₁ and m ₃₂ are each independently an integer of 0 to 2, preferably 0 or 1. m ₃₃ and m ₃₄ are each independently an integer of 0 to 2, It is preferably 0 or 1. R ₃₁ to R ₃₃ are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms. ₃₁ to p ₃₃ are an integer of 0 to 4, and preferably 0. L ₃₁ is a single bond, an ether group, a carbonyl group or an alkylene group having 1 to 4 carbon atoms.)

Since R ₃ is a divalent group having at least one aromatic ring and having 6 to 22 carbon atoms, m ₃₁ , m ₃₂ , R ₃₁ and p ₃₁ in the general formula (R3-1) represent the general formula The divalent group represented by (R3-1) is selected so that the carbon number of the divalent group falls within the range of 6 to 22.

Similarly, L ₃₁ , m ₃₃ , m ₃₄ , R ₃₂ , R ₃₃ , p ₃₂ and p ₃₃ in the general formula (R3-2) represent a carbon of a divalent group represented by the general formula (R3-2). The number is chosen to be in the range 12-22.

X ₃ is defined in the same manner as X ₁ in the general formula (1). Preferred aspects of X ₃ is the same as _{X 1.}

Examples of the structural unit that the resin (A) can contain in addition to the structural units represented by the general formulas (1) to (3) include a structural unit represented by the general formula (4). Can be.

(Wherein R ₄ is a divalent group containing —SO ₂ — or —Si (R _x ) (R _y ) O—, and R _x and R _y are each independently a chain having 1 to 3 carbon atoms. X ₄ is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.)

X ₄ is defined in the same manner as X ₁ in the general formula (1). Preferred aspects of X ₄ is the same as _{X 1.}

The resin (A) may be either an amorphous or crystalline thermoplastic polyimide resin, and is preferably a crystalline thermoplastic polyimide resin from the viewpoint of moldability.

融点 The melting point of the resin (A) is preferably 390 ° C or lower, more preferably 360 ° C or lower, and further preferably 330 ° C or lower, from the viewpoint of heat resistance and moldability. The lower limit of the melting point is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and further preferably 270 ° C. or higher. Further, the glass transition temperature (Tg) is preferably 170 ° C. or higher, more preferably 200 ° C. or higher, and further preferably 230 ° C. or higher, from the viewpoint of heat resistance. The melting point and the glass transition temperature (Tg) were measured using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min. The temperature can be measured by lowering the temperature at 10 ° C./min, cooling to 20 ° C., allowing the mixture to stand for 1 minute, and then heating again at a rate of 10 ° C./min.

From the viewpoint of the moldability of the obtained resin composition, the MFR value of the resin (A) is preferably 0.1 g / 10 min or more, and preferably 1 g / min, measured at 350 ° C. under a load of 2.16 kg. More preferably, it is 10 minutes or more. On the other hand, from the viewpoint of heat resistance, the MFR value measured under the conditions of 350 ° C. and a load of 2.16 kg is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, and more preferably 10 g / 10 min or less. Is more preferable. Further, since the molecular weight and the melt viscosity are correlated, the MFR value can be used as an index of the molecular weight of the resin (A). The MFR value of the resin (A) can be measured according to JIS K7210.

形状 The shape of the resin (A) is not particularly limited as long as it can be melt-kneaded, and any of a powder, a granule, and a pellet can be used.

The content of the resin (A) in the polyimide resin composition is usually 50 to 99% by mass, preferably 60 to 97% by mass, more preferably 70 to 97% by mass based on 100% by mass of the total amount of the polyimide resin composition. 95% by mass.

(Phosphazene compound (B))
The phosphazene compound (B) is a compound represented by the following formula (5). The polyimide resin composition of the present invention is characterized in that the composition contains a compound represented by the formula (5). Since the above compound does not elute even when added to the thermoplastic polyimide resin composition, the flame retardant effect can be maintained. Therefore, the compound represented by the formula (5) can be suitably used as a flame retardant for a thermoplastic polyimide resin composition.

The compound represented by the formula (5) has been reported to be used as a silver halide photographic light-sensitive material (JP-A-2002-169243), a flame retardant for polyester (US Pat. No. 3,865,783) and the like. Is a substance.

化合物 The compound represented by the formula (5) can be produced by a known production method. For example, as shown in the following reaction formula-1, the compound represented by the formula (5) can be produced by the method described in US Pat. No. 3,356,695.

ヘキサ The hexachlorocyclotriphosphazene represented by the formula (6) can be produced by a known method, that is, a production method based on a reaction between phosphorus pentachloride and ammonium chloride. Also, commercially available products can be used.

塩基 Examples of the base in Reaction Formula-1 include alkali metal salts and amine compounds, and preferred are alkali metal salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate.

化合物 The compound represented by the formula (5) can be obtained, for example, by reacting hexachlorocyclotriphosphazene (6) with 2,2′-biphenol (7) in a solvent such as monochlorobenzene. The 2,2'-biphenol (7) is preferably used in an amount of about 3 mol per 1 mol of hexachlorocyclotriphosphazene (6). The reaction temperature is preferably about 20 to 140 ° C., and the reaction time is preferably about 0.5 to 20 hours.

The shape of the phosphazene-based compound (B) is not particularly limited as long as it can be melt-kneaded, and any of a powder, a granule, and a pellet can be used.

ポリイミド The polyimide resin composition of the present invention only needs to contain the compound represented by the formula (5).

The compounding amount of the compound represented by the formula (5) in the polyimide resin composition of the present invention is preferably about 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, per 100 parts by mass of the polyimide resin. Parts, more preferably about 5 to 30 parts by mass.

ポリイミド The polyimide resin composition of the present invention includes an embodiment in which a mixture represented by the following formula (8) containing the compound represented by the formula (5) is blended.

The mixture represented by the formula (8) is, for example, 50 to 90% by mass of a compound in which n is 3 in the formula (8) (compound represented by the formula (5)) in 100% by mass of the mixture. In (8), the compound in which n is 4 is 5 to 40% by mass, in Formula (8), the compound in which n is 5 is 0 to 30% by mass, and in Formula (8), the compound in which n is 6 to 15 is used. It is preferable to contain 0 to 20% by mass.

When the compound represented by the formula (5) is blended with the polyimide resin composition of the present invention in the form of a mixture represented by the formula (8), the mixture represented by the formula (8) is replaced with the compound represented by the formula (8) ) In the mixture represented by the formula (5) is preferably about 1 to 50 parts by weight, more preferably about 1 to 50 parts by weight, based on 100 parts by weight of the polyimide resin. The compounding amount may be about 3 to 40 parts by mass, and more preferably about 5 to 30 parts by mass.

The mixture represented by the formula (8) is obtained by mixing the mixture represented by the formula (9) with 2,2′- instead of using hexachlorocyclotriphosphazene in the method for producing the compound represented by the formula (5). It can be produced by reacting biphenol with a base. In the mixture represented by the formula (9), 50 to 90% by mass of the compound (the compound represented by the formula (6)) where m is 3 in the formula (9), and 4% in the formula (9). 5 to 40% by mass of a compound represented by the formula (9), 0 to 30% by mass of a compound wherein m = 5 in the formula (9), and 0 to 20% by mass of a compound wherein m is 6 to 15 in the formula (9). Is preferred. The mixture represented by the formula (9) can be produced by a known method. For example, JP-A-57-87427, JP-B-58-19604, JP-B-61-1363, or JP-A-61-1363. It can be produced according to the method described in JP-B-62-20124 and the like.

(N represents an integer of 3 to 15)

(M represents an integer of 3 to 15)

The content of the phosphazene-based compound (B) in the polyimide resin composition is usually 1 to 50% by mass, preferably 3 to 40% by mass, more preferably 100% by mass based on the total amount of the polyimide resin composition. 5 to 30% by mass.

(Other compounding materials (C))
The polyimide resin composition of the present invention can contain another compounding material (C) from the viewpoint of imparting desired performance to the resin (A). Other compounding materials (C) include a dripping inhibitor, a fibrous reinforcing material, a plate-like reinforcing material, a solid lubricant, a flame retardant other than the phosphazene compound (B), a coloring agent, an antioxidant, and an ultraviolet absorber. , A conductive agent, a flame retardant aid, a crystal nucleating agent, a plasticizer, a release agent, an antistatic agent, a coloring inhibitor, a gelling agent and the like.

As an anti-dripping agent, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer Coalesced (ETFE), poly (trifluorochloroethylene) (CTFE), polyvinylidene (PVdF), inorganic fillers and the like. As fibrous reinforcing materials, aramid fiber, polyphenylene benzoxazole (PBO) fiber, glass fiber, carbon fiber, alumina fiber, boron fiber, silicon carbide fiber, potassium titanate fiber, wollastonite fiber, aluminum borate fiber, boric acid Magnesium fiber, zonotolite fiber, zinc oxide fiber, basic magnesium sulfate fiber, and the like. Examples of the plate-like reinforcing material include mica, mica, sericite, illite, talc, kaolinite, montmorillonite, boehmite, smectite, vermiculite, titanium dioxide, potassium titanate, lithium potassium titanate, and boehmite. As solid lubricants, polyolefin resins such as polytetrafluoroethylene (PTFE), low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultrahigh-molecular-weight polyethylene, graphite, molybdenum disulfide, and tungsten disulfide , Boron nitride and the like. As a flame retardant other than the phosphazene-based compound (B), phosphate ester, condensed phosphate ester, inorganic phosphorus-based flame retardant, halogen-based flame retardant, silicone-based flame retardant, metal oxide-based flame retardant, metal hydroxide-based flame retardant Flame retardants, organic metal salt-based flame retardants, nitrogen-based flame retardants, boron compound-based flame retardants, and the like. Examples of the coloring agent include pigments such as carbon black and titanium oxide, and dyes. Examples of the antioxidant include a phenol antioxidant, a sulfur antioxidant, a phosphorus antioxidant, a copper antioxidant, and an amine antioxidant. Examples of the UV absorber include a benzophenone-based UV absorber, a benzotriazole-based UV absorber, a triazine-based UV absorber, and a thyristylate-based UV absorber. Examples of the conductive agent include a carbon-based conductive agent, a metal-based conductive agent, a metal oxide-based conductive agent, and a surfactant. One or more of these may be added to the polyimide resin composition of the present invention.

When the polyimide resin composition of the present invention contains the above-mentioned other compounding material (C), the compounding amount is such that the effect of the other compounding material (C) is exhibited, and the molding processability and heat resistance of the resin (A) have From the viewpoint of maintaining the property, the total amount is preferably 0.01 to 40% by mass, more preferably 0.1 to 30% by mass, and still more preferably 1 to 30% by mass in the total amount of 100% by mass of the polyimide resin composition. 20% by mass. In addition, "the compounding amount of other compounding materials (C)" means the total content of other compounding materials used for the polyimide resin composition.

(Method for producing resin composition)
The polyimide resin composition of the present invention comprises mixing and heating (particularly, melting) the thermoplastic polyimide resin (A), the phosphazene-based compound (B), and if necessary, other components of the compounding material (C). Kneading).

A known melt-kneading device such as a twin-screw extruder can be used for the melt-kneading. Specifically, (1) a method in which each component is preliminarily mixed by a mixer (a tumbler, a Henschel mixer or the like), melt-kneaded by a melt-kneading apparatus, and pelletized by a pelletizing means (a pelletizer or the like); (2) A method of preparing a masterbatch of a desired component, mixing other components as necessary, and melt-kneading with a melt-kneading apparatus to form pellets; (3) a method of supplying each component to a melt-kneading apparatus to form pellets; Can be manufactured.

加工 The processing temperature in the melt kneading is not particularly limited as long as the thermoplastic resin can be melted. Usually, the cylinder temperature of the melt-kneading apparatus used for melt-kneading is adjusted to this range. Thus, the resin composition used in the present invention, which exhibits the desired effects, is produced.

<Molded body>
The molded article of the present invention contains the polyimide resin composition containing the various components described above. Since the resin (A) is a resin that can be melt-molded by heating, a molded article (molded article) can be produced by thermoforming the polyimide resin composition of the present invention containing the resin (A). As the thermoforming method, any method may be used as long as it is a molding method that goes through a heat melting step. Examples of the thermoforming method include injection molding, insert molding, compression molding, extrusion molding, blow molding, and inflation molding.

方法 The method for producing a molded article of the present invention preferably includes a step of thermoforming the polyimide resin composition of the present invention at 300 to 400 ° C.

成形 Examples of the shape of the molded article of the present invention include various shapes such as a film, a fiber, a round bar, a square bar, a sphere, a pipe, and a tube. Further, a molding method obtained by combining the above-described molding methods can be adopted.

用途 The use of the molded article of the present invention is not particularly limited, and it can be applied particularly to any use requiring heat resistance and flame retardancy. Usable applications include, for example, automotive parts such as washers, needle bearings, seal rings, gears, ABS parts, clutch rings; various bearings such as automotive bearings, copier bearings; copiers, printers, facsimiles, and the like. Fusing belts or intermediate transfer belts for various electrophotographic image forming apparatuses such as multifunction devices; surface mounting electronic members; condenser gaskets; optical connectors; flexible substrates; copper-clad laminates; multilayer printed wiring boards; Can be

Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following embodiments at all, and can be implemented with appropriate changes within a scope that does not change the gist of the present invention.

The thermoplastic polyimide resin and phosphazene-based compound used in Examples and Comparative Examples are specifically as follows.

(Thermoplastic polyimide resin)
Thermoplastic polyimide resin (A-1): melting point 319 ° C., glass transition temperature 178 ° C., MFR value 3.2 g / 10 min, manufactured by Mitsubishi Gas Chemical Company, Inc., trade name “Serprim TO65S”

The melting point and glass transition temperature of the thermoplastic polyimide resin were determined by using a differential calorimeter (trade name: "DSC7000X", manufactured by Hitachi High-Tech Science Co., Ltd.), placing 10 mg of the sample in an aluminum cell for measurement, and flowing nitrogen gas at 100 ml / min. Under the conditions, the temperature was raised from room temperature to 360 ° C. at a rate of 10 ° C./min, the sample was cooled to 20 ° C. at a rate of 10 ° C./min, held for 1 minute, and then heated again at a rate of 10 ° C. The temperature was raised to 360 ° C./min and measured.

(4) The MFR value of the thermoplastic polyimide resin was measured at 350 ° C. for 5 minutes, under a load of 2.16 kg according to JIS K7210.

(Phosphazene compound)
As the phosphazene-based compound, the compound (B-1) produced in Production Example 1 below and a commercially available compound (B-2) (manufactured by Wako Pure Chemical Industries, Ltd.) were used.

(Production of hexachlorocyclotriphosphazene)
A 1 L flask equipped with a reflux cooling device was charged with 500 ml of monochlorobenzene, 873.6 g of phosphorus pentachloride and 224.3 g of ammonium chloride, and refluxed for 5 hours. After the completion of the reflux, heating was stopped, filtration and distillation were performed to obtain 483 g of hexachlorocyclotriphosphazene, which was used in the following production examples.

(Production Example 1: Production of compound (B-1))
In a 5 L flask equipped with a Dean-Stark apparatus, a monochlorobenzene solution (1064.7 g, 2.5 mol) containing 2,2′-biphenol (491.1 g, 2.6 mol) and 26.8 mass% of cyclohexachlorotriphosphazene was added. A 48% aqueous sodium hydroxide solution (441.6 g, 5.3 mol) and monochlorobenzene (2.3 L) were added, and a nitrogen gas was flown thereinto, followed by heating under reflux for 12 hours. After the reflux, heating was stopped, deionized water (1.2 L) was added to the remaining reaction mixture, and the mixture was stirred for 2 hours. The crystals precipitated in the reactor were separated, washed with deionized water and methanol, and dried to obtain a white solid (413.88 g).

Examples 1 and 2, and Comparative Examples 1 and 2
The thermoplastic polyimide resin and the phosphazene-based compound were melt-kneaded in a mixing ratio shown in Table 1 using a twin-screw extruder to produce pellets. In addition, the cylinder temperature of the twin-screw extruder was 350 ° C.

ペレット UL pellets (length: 127 mm, width: 12.7 mm, thickness: 1.6 mm) were formed from the obtained pellets by an injection molding machine, and used as evaluation samples. The molding was performed at a cylinder temperature of the injection molding machine of 350 ° C. and a mold temperature of 170 ° C.

Evaluation method (kneading and moldability)
A sample that could be melt-kneaded and injection-molded by a twin-screw extruder without any problem and produced an evaluation sample was evaluated as “produced”. In the melt-kneading of the twin-screw extruder, the strand could not be taken out immediately after the start of kneading, foamed violently around the die, and could not be extruded. The results are shown in Table 1.

(Flame retardance)
The obtained UL test pieces were evaluated according to the UL-94 test method, and the results are shown in Table 1.

(Dissolution degree)
The obtained UL test piece (molded product) was heated in an oven in air at 120 ° C. for 600 hours. After measuring the mass of the molded body after heating, wiping out the eluted matter adhered to the molded body surface with Kimwipe (registered trademark) with acetone, and after sufficiently drying the molded body surface, the mass of the molded body was measured again. The elution degree was calculated from the following equation. The results are shown in Table 1.

Dissolution degree [%] = A / B × 100
A = (Massed body before wiping with acetone)-(Massed body after wiping with acetone)
B = (Molded body mass before wiping with acetone)

(Mass loss rate)
The raw materials used in the examples and the comparative examples, and the pellets obtained in the examples 1 and 10 mg, each of which was 10 mg, were measured using a differential thermogravimetric simultaneous measuring device (trade name “TG / DTA6300” manufactured by SII Corporation). The mass change was measured when the temperature was raised from room temperature to 500 ° C. at a rate of 10 ° C./min under a nitrogen flow of 200 ml / min, and the mass reduction rate was calculated from the following equation. The results are shown in Table 2.

Mass reduction rate [%] = C / D × 100
C = (sample mass at 350 ° C.) − (Sample mass at 150 ° C.)
D = (mass of sample at 150 ° C.)

測定 From the results of the measurement of the mass loss rate, it is understood that the resin composition of the present invention and the molded product thereof are excellent in thermal stability. This effect is not limited to the polyimide resin, and is similarly observed in other thermoplastic resin compositions.

Claims

A polyimide resin composition containing a thermoplastic polyimide resin (A) and a phosphazene-based compound (B), wherein the phosphazene-based compound (B) is a compound represented by the following formula (5).
2. The polyimide resin composition according to claim 1, wherein the thermoplastic polyimide resin (A) is a polymer having one or more structural units represented by the following general formulas (1) to (3).

(Wherein, R 1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure. X 1 is a 4-6 group containing 6 to 30 carbon atoms containing at least one aromatic ring. Is a valence group.)

(In the formula, R 2 is a divalent chain aliphatic group having 5 to 20 carbon atoms. X 2 is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.)

(Wherein, R 3 is a divalent group having 6 to 22 carbon atoms containing at least one aromatic ring. X 3 is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring. is there.)
3. The thermoplastic resin composition according to claim 2, wherein the total content of the structural units represented by the general formulas (1) to (3) is 50 to 100 mol% with respect to all the structural units constituting the thermoplastic polyimide resin (A). Polyimide resin composition.
ポリイミド The polyimide resin composition according to any one of claims 1 to 3, wherein the thermoplastic polyimide resin (A) has a glass transition temperature of 170 ° C or higher.
ポリイミド The polyimide resin composition according to any one of claims 1 to 4, wherein the melting point of the thermoplastic polyimide resin (A) is 390 ° C or less.
The polyimide resin composition according to any one of claims 1 to 5, wherein the content of the thermoplastic polyimide resin (A) is 50 to 99% by mass based on 100% by mass of the total amount of the polyimide resin composition.
The polyimide resin composition according to any one of claims 1 to 6, wherein the content of the phosphazene-based compound (B) is 1 to 50% by mass based on 100% by mass of the total amount of the polyimide resin composition.
(8) A molded article produced using the polyimide resin composition according to any one of (1) to (7).
The molded article according to claim 8, which is in the form of a film.
(8) A method for producing a molded product, comprising a step of thermoforming the polyimide resin composition according to any one of (1) to (7) at 300 to 400 ° C.