JP2008127481A - Flame retardant copolymer composition and resin sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that is excellent in thermoconductivity, heat resistance, flexibility and flame retardancy and hardly suffers from color changes during retention under heating, and a resin sheet and a molded item for heat dissipation obtained using the same. <P>SOLUTION: The copolymer composition comprises a hydrogenated copolymer (1) having a specific structure compounded in a specific amount and/or a modified hydrogenated copolymer (2) having a specific structure, zinc oxide (3) having a nuclear part and a needle-like crystal part extending from the nuclear part to four different axial directions, a phosphorous flame-retardant (4) and a paraffin oil (5). The resin sheet is composed of the copolymer composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention provides a resin composition having excellent thermal conductivity, heat resistance and flexibility, and having excellent flame retardancy and moldability in order to dissipate heat generated from components such as electronic devices. The present invention relates to a resin sheet and a molded body for heat dissipation.

  Conventionally, with the spread of digital home appliances, there is an increasing demand for higher speed and higher functionality of electrical components and electronic devices. However, in these electronic components and electronic devices, electronic elements such as LSIs and CPUs that perform electronic control have increased power consumption due to an increase in the degree of integration of computers and an increase in operation speed. Therefore, heat dissipation measures are indispensable. For heat dissipation in general electronic equipment, a heat sink or the like is attached, and the heat sink is forcibly cooled by a cooling fan or the like. Small devices such as notebook personal computers and electronic parts mounted at high density have limitations such as a small installation space such as a cooling fan, and measures against heat radiation have been taken by applying silicon grease. In addition, in order to meet the demand for higher performance of electronic components, the number of cases using heat dissipation sheets is increasing. The heat-dissipating sheet is used for the purpose of effectively transferring heat to the cooling component by attaching a close contact between the two when the cooling component such as a heat sink is attached to the heating element.

In recent years, in each application, there is a demand for a heat-dissipating molded body for the purpose of diffusing heat and a heat-dissipating resin sheet.
Conventionally, heat-radiation molded bodies and sheets are obtained by filling a material based on silicon rubber or silicon gel sheet with a filler having relatively high thermal conductivity.
However, since the silicon rubber sheet itself is expensive, a vulcanization process is necessary, and the process management is complicated. Furthermore, since low molecular siloxane is contained in the resin, low molecular siloxane gas is generated when used attached to a heating element, and the gas adheres to electrode contacts and the like to generate silicon dioxide. This can cause contact failure.

In addition, a heat-dissipating sheet may be used between a heat-generating body such as a CPU on the electronic substrate and a heat-dissipating body such as a heat sink. Insufficient heat dissipation efficiency cannot be obtained. In addition, if the heat resistance of the heat dissipation sheet is insufficient, the sheet may be deteriorated while the room temperature state and the high temperature state are repeated inside the electronic device.
In addition, heat dissipation sheets may be used for internal parts of electrical and electronic equipment, but from the viewpoint of safety, flame retardancy is required, and in recent years due to the use of non-halogen flame retardants. There are an increasing number of cases where environmentally friendly flame resistance is required.
On the other hand, it has been proposed to add zinc oxide whisker to the resin. This is to impart conductivity to the resin composition and to increase the mechanical strength of the resin. When a polypropylene resin used as a resin is used, the flexibility is insufficient. Moreover, the flame retardance which considered the environment is not provided (patent documents 1 and 2).

In addition, it has been proposed to add a reinforcing filler to a hydrogenated copolymer obtained by hydrogenating a copolymer comprising a conjugated diene and a vinyl aromatic. This is intended to improve the abrasion resistance and mechanical strength of the resin composition. When ordinary zinc oxide is used as the reinforcing filler, the heat dissipation is insufficient and the environment is taken into consideration. Flame retardancy is not imparted (Patent Document 3).
In addition, it has been proposed to incorporate thermally conductive particles such as alumina into a styrene thermoplastic elastomer. This is intended to improve the heat dissipation of the resin composition, but is insufficient to exhibit both flexibility and heat dissipation, and has not been given flame retardancy considering the environment (patent) Reference 4).
JP-A-1-225663 Japanese Patent Publication No. 7-51646 JP 2003-277560 A JP 2002-206030 A

  The present invention has been made in order to solve the problems of the heat conductive material as described above, has excellent heat conductivity and heat resistance, and further has excellent flame resistance while maintaining flexibility. An object of the present invention is to provide a copolymer composition excellent in the property of little change in color when heated and retained, a resin sheet using the same, and a molded product for heat dissipation.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific hydrogenated copolymer and / or a modified hydrogenated copolymer, a core part, and a needle-like crystal extending from the core part in four axial directions. A copolymer composition containing zinc oxide having a part, a phosphorus flame retardant, and paraffinic oil, and a resin sheet comprising the copolymer composition have excellent thermal conductivity and heat resistance, and further flexibility It has been found that it is excellent in flame retardancy and has little change in color during heat retention, and is optimal for use in heat-dissipating molded articles and heat-dissipating sheets, and has led to the present invention. .

That is, the present invention
1. Hydrogenated copolymer (1) satisfying the following (a) to (d) by adding hydrogen to a copolymer comprising a conjugated diene and a vinyl aromatic and / or a copolymer comprising a conjugated diene and a vinyl aromatic A styrenic soft resin comprising a modified hydrogenated copolymer (2) satisfying the following (a) to (d) in which hydrogen is added to and at least one atomic group having at least one functional group is bonded: And zinc oxide (3) having needle-like crystal parts extending in different four-axis directions from the core part, phosphorus flame retardant (4), and paraffin oil (5). ) To (D) are satisfied.
(A) The content of vinyl aromatic units is more than 50% by mass and 90% by mass or less.
(B) The amount of the polymer block made of vinyl aromatic is 40% by mass or less.
(C) The weight average molecular weight is 50,000 to 1,000,000.
(D) The hydrogenation rate of the double bond based on the conjugated diene is 10% or more.
(1) + (2) + (3) + (4) + (5) = 100 mass%,
(A) (1) + (2) + (5) = 5-85 mass%
(B) 0 <(5) / [(1) + (2)] ≦ 2 (mass ratio)
(C) (3) = 10 to 90% by mass
(D) (4) = 5-40% by mass

2. The modified hydrogenated copolymer (2) is characterized in that at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. 1. The copolymer composition described in 1.
3. 1. The amount of the polymer block composed of vinyl aromatic in the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2) is less than 10% by mass. Or 2. The copolymer composition described in 1.
4). 1. The amount of the polymer block composed of vinyl aromatic in the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2) is 10 to 40% by mass. Or 2. The copolymer composition described in 1.

5. 1. Hydrogenated copolymer (1) and / or modified hydrogenated copolymer (2) is a hydrogenated product of a copolymer having at least one structure selected from the following general formula. ~ 4. The copolymer composition according to any one of the above.
(I) B
(B) B-A
(C) B-A-B
(D) (B-A) _m -X
(E) (B-A) _n- X-A _p
(Here, B is a random copolymer block of conjugated diene and vinyl aromatic, A is a vinyl aromatic polymer block, m is an integer of 2 or more, and n and p are each 1 or more. (It is an integer. X represents a coupling agent residue.)
6). 1. The modified hydrogenated copolymer (2) is characterized in that at least one atomic group having at least one functional group selected from the following formula is bonded. ~ 5. Copolymer composition as described in any one of these.

(In the above formula, R ^{1 to} R ⁴ are hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. 24 hydrocarbon groups.
R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. In the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , elements such as oxygen, nitrogen, and silicon are bonded in a bonding mode other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group. May be. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms. )

7. A modified hydrogenated copolymer (2) is obtained by adding a functional group-containing modifier to the living terminal of a copolymer of a conjugated diene and a vinyl aromatic obtained using an organolithium compound as a polymerization catalyst. 1. The copolymer is hydrogenated. ~ 6. Copolymer composition as described in any one of these.

8). Hydrogenated copolymer (1) and / or modified hydrogenated copolymer (2), zinc oxide having needle-like crystal part (3), phosphorus flame retardant (4), paraffinic oil (5), 1. It contains 10 to 400 W / mK heat conductive filler (6) other than zinc oxide (3) having an acicular crystal part, and satisfies the following (A) to (E). ~ 7. Copolymer composition as described in any one of these.
(1) + (2) + (3) + (4) + (5) + (6) = 100 mass%,
(A) (1) + (2) + (5) = 5-85 mass%
(B) 0 <(5) / [(1) + (2)] ≦ 2 (mass ratio)
(C) (3) + (6) = 10 to 90% by mass
(D) 0 <(6) / (3) ≦ 1
(E) (4) = 5-40% by mass

9. Hydrogenated copolymer (1) and / or modified hydrogenated copolymer (2), zinc oxide (3) having acicular crystal parts, phosphorus flame retardant (4), paraffinic oil (5), acicular The heat conductive filler (6) other than zinc oxide (3) having a crystal part further contains a metal hydroxide flame retardant (7), and satisfies the following (A) to (F): 8. The copolymer composition described in 1.
(1) + (2) + (3) + (4) + (5) + (6) + (7) = 100 mass%,
(A) (1) + (2) + (5) = 5-85 mass%
(B) 0 <(5) / [(1) + (2)] ≦ 2 (mass ratio)
(C) (3) + (6) = 10 to 90% by mass
(D) 0 <(6) / (3) ≦ 1
(E) (4) + (7) = 5-40% by mass
(F) 0 <(7) / (4) ≦ 2

10. 7. The heat conductive filler (6) is at least one selected from silicon nitride, aluminum nitride, silicon carbide, and boron nitride. Or 9. The copolymer composition described in 1.
11. The phosphorus content of the phosphorus flame retardant (4) is 8 to 25% by mass. -10. Copolymer composition as described in any one of these.
12 The phosphorus flame retardant (4) is phosphazene. ~ 11. Copolymer composition as described in any one of these.
13.1. -12. The resin sheet which consists of a copolymer composition as described in any one of these.
14.1. -12. Use of the copolymer composition according to any one of the above for a flame-retardant heat dissipation molded article.

  According to the present invention, a copolymer composition having excellent thermal conductivity and heat resistance, excellent in flame retardancy, and excellent in properties such as little color change at the time of heat retention while maintaining flexibility and A resin sheet using the same and a molded body for heat dissipation can be provided.

The present invention relates to a hydrogenated copolymer (1) and / or a modified hydrogenated copolymer (2) having a specific structure and blending amount, a core part, and acicular crystals extending from the core part in different four-axis directions. A zinc oxide (3) having a part, a phosphorus-based flame retardant (4), and a paraffinic oil (5), and a resin sheet made of the copolymer composition.
The hydrogenated copolymer (1) and / or modified hydrogenated copolymer (2) of the present invention (hereinafter referred to as a hydrogenated copolymer, etc.) is a copolymer comprising a conjugated diene and a vinyl aromatic, A hydrogenated copolymer obtained by adding hydrogen.

  In the present invention, the content of vinyl aromatic units in the hydrogenated copolymer or the like is more than 50% by mass and 90% by mass or less, preferably more than 50% by mass and 88% by mass or less, more preferably more than 50% by mass and 86% by mass. It is below mass%. Use of the vinyl aromatic unit content within the range specified by the present invention provides a copolymer composition of the present invention that is rich in flexibility, excellent in abrasion resistance, scratch resistance, strength, and the like. Is necessary for. The hydrogenated copolymer of the present invention may contain a hydrogenated vinyl aromatic unit. This hydrogenated vinyl aromatic unit is also contained in the hydrogenated copolymer. It shall be included in the vinyl aromatic content. In the present invention, the content of vinyl aromatic units in the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2) is grasped by the vinyl aromatic unit content in the copolymer before hydrogenation. May be.

  In the hydrogenated copolymer or the like used in the present invention, the content of the polymer block composed of vinyl aromatic is required to be 40% by mass or less, preferably 3 to 40% by mass, more preferably 5 to 35% by mass. is there. When the amount of the polymer block made of vinyl aromatic is 40% by mass or less, since the polymer block made of vinyl aromatic is flexible, the flexibility of the composition is improved. In the present invention, when it is desired to obtain a more flexible composition, the content of the polymer block made of vinyl aromatic is preferably less than 10% by mass, more preferably less than 8% by mass, and even more preferably 5% by mass. Is encouraged to be less. Moreover, in obtaining the copolymer composition of the present invention, when a hydrogenated copolymer or the like excellent in blocking resistance is preferable, the polymer block composed of vinyl aromatic is preferably 10 to 40% by mass, More preferably, it is 13-37 mass%, More preferably, it is 15-35 mass%.

The content of the polymer block composed of vinyl aromatic is measured by, for example, a method in which osmium tetroxide is used as a catalyst to oxidatively decompose the copolymer before hydrogenation with tertiary butyl hydroperoxide (IM KOLTHOFF, et al. , J. Polym. Sci. 1, 429 (1946)), the weight of the vinyl aromatic polymer block component (however, the vinyl aromatic polymer component having an average degree of polymerization of about 30 or less is excluded). Can be obtained from the following equation.
Vinyl aromatic block mass (% by mass)
= {(Polymer block mass consisting of vinyl aromatic in copolymer before hydrogenation / Mass of copolymer before hydrogenation)} × 100

  In the present invention, the vinyl aromatic block ratio in the hydrogenated copolymer or the like (the block ratio refers to the ratio of the content of the vinyl aromatic polymer block to the total vinyl aromatic content in the copolymer). Is preferably less than 50% by weight, more preferably 20% by weight or less, and even more preferably 18% by weight or less in order to obtain a more flexible composition.

  The weight average molecular weight of the hydrogenated copolymer used in the present invention is 50,000 to 1,000,000, preferably 100,000 to 800,000, more preferably 130,000 to 500,000. In the case of using a hydrogenated copolymer having a polymer block content of 10 to 40% by mass made of vinyl aromatic, the weight average molecular weight is preferably 100,000 to 500,000, more preferably 130,000 to 400,000. More preferably, it is 150,000 to 300,000. When the weight average molecular weight is less than 50,000, the mechanical strength is inferior, and when it exceeds 1,000,000, the molding processability is inferior. Furthermore, when the weight average molecular weight is 50,000 to 1,000,000, the content of low molecular weight components is small, so that there are few volatile components.

  The molecular weight distribution (Mw / Mn) (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn)) of the hydrogenated copolymer used in the present invention is 1.01 to 8 in terms of moldability. 0.0 is preferred, more preferably 1.1 to 6.0, and even more preferably 1.1 to 5.0. The shape of the molecular weight distribution measured by gel permeation chromatography (GPC) is not particularly limited, and may have a polymodal molecular weight distribution having two or more peaks (peaks), but there is only one peak. It preferably has a monomodal molecular weight distribution.

The hydrogenated copolymer used in the present invention is a hydrogenated product of a copolymer comprising a conjugated diene and a vinyl aromatic, and the total hydrogenation rate of unsaturated double bonds based on the conjugated diene in the copolymer is 10% or more is necessary, preferably 20% or more, and more preferably 30% or more. When the hydrogenation rate is 10% or less, the heat resistance is inferior, for example, the flexibility, strength and elongation of the composition matrix are reduced due to thermal deterioration. In particular, when obtaining a composition having excellent weather resistance, the hydrogenation rate is preferably 75% or more, more preferably 85% or more, and further preferably 90% or more.
Furthermore, in the hydrogenated copolymer used in the present invention, when obtaining a composition having particularly excellent thermal stability, the hydrogenation rate of the vinyl bond is preferably 85% or more, more preferably 90% or more, still more preferably Is encouraged to be over 95%.
Here, the hydrogenation rate of vinyl bonds refers to the proportion of vinyl bonds that have been hydrogenated among the vinyl bonds in the conjugated diene incorporated in the copolymer before hydrogenation.
The hydrogenation rate of the aromatic double bond based on the vinyl aromatic in the copolymer is not particularly limited, but the hydrogenation rate is preferably 50% or less, more preferably 30% or less, and still more preferably 20 % Or less.

  The hydrogenated copolymer or the like used in the present invention is preferably a hydrogenated product having substantially no crystallization peak in the temperature range of −50 to 100 ° C. in the differential scanning calorimetry (DSC method). Here, substantially no crystallization peak exists in the temperature range of −50 to 100 ° C. when no peak due to crystallization appears in this temperature range, or when a peak due to crystallization is observed. However, the crystallization peak heat quantity in the crystallization is preferably less than 3 J / g, more preferably less than 2 J / g, still more preferably less than 1 J / g, and particularly preferably no crystallization peak heat quantity.

In the present invention, the structure of the hydrogenated copolymer or the like is not particularly limited, and any structure can be used. However, what is particularly encouraged has at least one structure selected from the following general formulas (i) to (e). It is a hydrogenated product of a copolymer. The hydrogenated copolymer or the like used in the present invention may be an arbitrary mixture comprising a hydrogenated copolymer having a structure represented by the following general formulas (i) to (e). Further, a polymer made of vinyl aromatic may be mixed with a hydrogenated copolymer or the like.
(I) B
(B) B-A
(C) B-A-B
(D) (B-A) _m -X
(E) (B-A) _n- X-A _p
(Here, B is a random copolymer block of conjugated diene and vinyl aromatic, A is a vinyl aromatic polymer block, m is an integer of 2 or more, and n and p are each 1 or more. (It is an integer. X represents a coupling agent residue.)
In the general formula, the vinyl aromatics in the random copolymer block B may be distributed uniformly or in a tapered shape. In the copolymer block B, a plurality of portions where vinyl aromatics are uniformly distributed and / or portions where tapes are distributed may coexist. M is 2 or more, preferably an integer of 2 to 10, and n and p are each 1 or more, preferably an integer of 1 to 10.

  In the present invention, the difference between the maximum value and the minimum value of the vinyl bond content in the copolymer chain before hydrogenation is preferably less than 10%, more preferably 8% or less, and even more preferably 6% or less. It is encouraged. The vinyl bonds in the copolymer chain may be distributed uniformly or in a tapered shape. Here, the difference between the maximum value and the minimum value of the vinyl bond content is the maximum value and the minimum value of the vinyl amount determined by the polymerization conditions, that is, the type and amount of the vinyl amount adjusting agent and the polymerization temperature.

  The difference between the maximum value and the minimum value of the vinyl bond content in the conjugated diene polymer chain can be controlled by, for example, the polymerization temperature during the polymerization of the conjugated diene or the copolymerization of the conjugated diene and the vinyl aromatic. When the type and amount of a vinyl amount modifier such as a tertiary amine compound or an ether compound is constant, the vinyl bond content incorporated into the polymer chain during polymerization is determined by the polymerization temperature. Therefore, a polymer polymerized isothermally becomes a polymer in which vinyl bonds are uniformly dispersed. In contrast, polymers polymerized at elevated temperatures become polymers with different vinyl bond contents, such as high vinyl bond content in the initial (polymerization at low temperature) and low vinyl bond content in the latter half (polymerization at high temperature). . A hydrogenated copolymer having a specific structure can be obtained by adding hydrogen to the copolymer having such a structure.

In the present invention, the content of the vinyl aromatic unit can be known using an ultraviolet spectrophotometer, an infrared spectrophotometer, a nuclear magnetic resonance apparatus (NMR), or the like. The amount of the polymer block made of vinyl aromatic can be known by the KOLTHOFF method described above. The vinyl bond content based on the conjugated diene in the copolymer before hydrogenation can be known using an infrared spectrophotometer (for example, the Hampton method), a nuclear magnetic resonance apparatus (NMR), or the like. Moreover, the hydrogenation rate of a hydrogenated copolymer etc. can be known using an infrared spectrophotometer, a nuclear magnetic resonance apparatus (NMR), etc.
In the present invention, the molecular weight of the hydrogenated copolymer or the like is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is obtained from a calibration curve obtained from the measurement of commercially available standard polystyrene ( The weight average molecular weight determined using the peak molecular weight of standard polystyrene). Similarly, the molecular weight distribution of a hydrogenated copolymer or the like can be determined from measurement by GPC.

In the present invention, a conjugated diene is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3. -Butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, etc., and particularly common ones include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more.
Examples of vinyl aromatics include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p. -Aminoethylstyrene etc. are mention | raise | lifted and these may use not only 1 type but 2 or more types.

  In the present invention, the microstructure of the conjugated diene portion (ratio of cis, trans, vinyl) in the copolymer before hydrogenation can be arbitrarily changed by using a polar compound or the like described later, and is not particularly limited. In general, when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond is preferably 5 to 80%, more preferably 10 to 60%, when isoprene is used as the conjugated diene, or 1 , 3-butadiene and isoprene are combined, it is recommended that the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is preferably 3 to 75%, more preferably 5 to 60%. The In the present invention, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene, the amount of 1,2-vinyl bonds) is Hereinafter referred to as vinyl bond.

  In the present invention, the copolymer before hydrogenation is obtained, for example, by anion living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane and n-octane, and alicyclic carbonization such as cyclohexane, cycloheptane and methylcycloheptane. Hydrogen, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

  In addition, as an initiator, an aliphatic hydrocarbon alkali metal compound, an aromatic hydrocarbon alkali metal compound, or an organic aminoalkali metal compound generally known to have anionic polymerization activity for conjugated dienes and vinyl aromatics The alkali metal is lithium, sodium, potassium or the like. Suitable organic alkali metal compounds are aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, a compound containing one lithium in one molecule, and a dilithium compound containing a plurality of lithiums in one molecule , Trilithium compounds, tetralithium compounds and the like.

  Specifically, n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, tolyl lithium, diisopropenylbenzene and sec- A reaction product of butyllithium, a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene can be used. Further, 1- (t-butoxy) propyllithium disclosed in US Pat. No. 5,708,092 and a lithium compound in which one to several molecules of isoprene monomer are inserted to improve its solubility, British Patent 2 Siloxy group-containing alkyllithium such as 1- (t-butyldimethylsiloxy) hexyllithium disclosed in US Pat. No. 5,241,239, amino group-containing alkyl disclosed in US Pat. No. 5,527,753 Aminolithiums such as lithium, diisopropylamidolithium and hexamethyldisilazide lithium can also be used.

Content of vinyl bond (1, 2 or 3, 4 bond) resulting from conjugated diene incorporated into polymer when copolymerizing conjugated diene and vinyl aromatic using organic alkali metal compound as polymerization initiator in the present invention In order to adjust the random copolymerizability between the conjugated diene compound and the vinyl aromatic, a tertiary amine compound or an ether compound can be added as a regulator. The tertiary amine compound is represented by the general formula R ¹ R ² R ³ N (where R ¹ , R ² and R ³ are hydrocarbon groups having 1 to 20 carbon atoms or a tertiary amino group. ).

  For example, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′— Tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N ′, N ″, N ″ -pentamethylethylenetriamine, N, N′-dioctyl-p-phenylenediamine, etc. .

The ether compound is selected from linear ether compounds and cyclic ether compounds, and the linear ether compound is an ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether or the like. And dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.
Cyclic ether compounds include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane, and alkyl ethers of furfuryl alcohol. Etc.

  In the present invention, the method of copolymerizing a conjugated diene and a vinyl aromatic using an organic alkali metal compound as a polymerization initiator may be batch polymerization, continuous polymerization, or a combination thereof. In particular, a continuous polymerization method is recommended for adjusting the molecular weight distribution to a preferable appropriate range. The polymerization temperature is generally 0 ° C. to 180 ° C., preferably 30 ° C. to 150 ° C. Although the time required for the polymerization varies depending on the conditions, it is usually within 48 hours, particularly preferably 0.1 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as the polymerization pressure is in a range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range. Furthermore, care must be taken so that impurities that inactivate the catalyst and living polymer, such as water, oxygen, and carbon dioxide, do not enter the polymerization system.

  In the present invention, a coupling reaction can be performed by adding a necessary amount of a bifunctional or higher functional coupling agent at the end of the polymerization. Any known bifunctional coupling agent may be used, and is not particularly limited. Examples thereof include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.

Further, any known trifunctional or higher polyfunctional coupling agent may be used without any particular limitation. For example, trihydric or higher polyalcohols, polyepoxy compounds such as epoxidized soybean oil, diglycidyl bisphenol A, general formula R _4-n SiX _n (where R is a hydrocarbon group having 1 to 20 carbon atoms, X halogen, n represents a halogenated silicon compound represented by 3 or 4), such as methyl silyl trichloride, t- butyl silyl trichloride, silicon tetrachloride and the like of these bromides formula R _4-n SiX _n (provided that , R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, n is 3 or 4), for example, a tin halide compound such as methyl tin trichloride, t-butyl tin trichloride, tin tetrachloride and other polyvalent halogens Compounds. Dimethyl carbonate or diethyl carbonate can also be used.

  In the present invention, a modified copolymer (2) in which a polar group-containing atomic group having a functional group is bonded to at least one polymer chain of the polymer is used as a copolymer. Examples of the polar group-containing atomic group include a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, and a carboxylic acid ester group. Amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, iso Examples thereof include an atomic group containing at least one polar group selected from a thiocyanate group, a silicon halide group, a silanol group, an alkoxysilicon group, a tin halide group, an alkoxytin group, a phenyltin group and the like.

The modified copolymer (2) can be obtained by reacting a compound having these polar group-containing atomic groups at the end of polymerization of the copolymer. As the compound having a polar group-containing atomic group, specifically, a modifying agent described in JP-B-4-39495 can be used. A preferred modified hydrogenated copolymer used in the present invention is a modified hydrogenated copolymer in which an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. A more preferable modified hydrogenated copolymer is a modified hydrogenated copolymer in which an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, and an amino group is bonded.
Such a modified hydrogenated copolymer is obtained by adding a functional group-containing modifier to the living end of a copolymer obtained by the above-described method using an organolithium compound as a polymerization catalyst, thereby adding a hydroxyl group to the copolymer. It can be obtained by adding hydrogen to a modified copolymer to which at least one atomic group having at least one functional group selected from an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded.

As another method for obtaining the modified copolymer (2), a copolymer obtained by reacting a hydrogenated copolymer before modification with an organic alkali metal compound such as an organic lithium compound (metalation reaction) and adding an organic alkali metal to the copolymer. And a method in which a functional group-containing modifier is added. Depending on the type of modifier, the hydroxyl group and amino group may generally be an organometallic salt at the stage of reaction of the modifier, but in that case, treatment with a compound having active hydrogen such as water or alcohol. By doing so, a hydroxyl group, an amino group, or the like can be obtained.
In the present invention, an atomic group preferable as an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group includes an atomic group selected from those represented by the following general formula: It is done.

(In the above formula, R ^{1 to} R ⁴ are hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. A hydrocarbon group having 24. R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. In the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , elements such as oxygen, nitrogen, and silicon are bonded in a bonding mode other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms.)

  In the present invention, it is used to obtain a modified hydrogenated copolymer in which at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. Examples of the modifying agent include the following.

  For example, tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidylorthotoluidine, γ-glycidoxyethyltrimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxy Examples include silane, γ-glycidoxypropyltriphenoxysilane, and γ-glycidoxypropylmethyldimethoxysilane.

  Γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxy Propylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycyl Sidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane and the like can be mentioned.

  Also, bis (γ-glycidoxypropyl) dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) di Butoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycidoxypropyl) methylmethoxysilane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) ) Methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxypropyl) methylphenoxysilane, and the like.

  Also, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, Examples thereof include bis (γ-methacryloxypropyl) dimethoxysilane, tris (γ-methacryloxypropyl) methoxysilane, and the like.

  Β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane and the like.

  Β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldi Propoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethyl Examples include methoxysilane and β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane.

  Furthermore, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane Β- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxy Examples include silane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, N-methylpyrrolidone and the like.

A functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group by reacting the above modifier with the living end of the copolymer obtained by the above-described method using an organolithium compound as a polymerization catalyst. A modified copolymer (2) in which the residue of the modifying agent to which the atomic group having at least one group is bonded is bonded.
In the present invention, the hydrogenated copolymer and the like can be obtained by hydrogenating the copolymer obtained before the hydrogenation or the modified copolymer obtained above. The hydrogenation catalyst is not particularly limited and is conventionally known (1) A supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A catalyst, (2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Ru, A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Rh or Zr is used.

  Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-39770, Japanese Patent Publication No. 1-53851, The hydrogenation catalyst described in Japanese Patent Publication No. 2-9041 can be used. A preferred hydrogenation catalyst is a mixture with a titanocene compound and / or a reducing organometallic compound. As the titanocene compound, a compound described in JP-A-8-109219 can be used. Specific examples thereof include (substitution) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton. Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

  The hydrogenation reaction is generally carried out in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and still more preferably 0.3 to 5 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.

  In the case of the modified hydrogenated copolymer (2) in the present invention, a partially unmodified hydrogenated copolymer may be mixed in the modified hydrogenated copolymer. The proportion of the unmodified hydrogenated copolymer mixed in the modified hydrogenated copolymer (2) is preferably 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less. In the solution of the hydrogenated copolymer and the like obtained as described above, the catalyst residue can be removed if necessary, and the hydrogenated copolymer and the like can be separated from the solution. Solvent separation methods include, for example, a method in which a polar solvent that is a poor solvent for a polymer such as acetone or alcohol is added to the solution after hydrogenation to precipitate and recover the polymer, a hydrogenated copolymer or modified water Examples thereof include a method in which the additive copolymer solution is poured into hot water with stirring and the solvent is removed by steam stripping, or a method in which the solvent is distilled off by directly heating the polymer solution.

In addition, stabilizers, such as various phenol type stabilizers, phosphorus type stabilizers, sulfur type stabilizers, and amine type stabilizers, can be added to the hydrogenated copolymer used in the present invention.
In the copolymer composition of the present invention, the hydrogenated copolymer (1) and the modified hydrogenated copolymer (2) can be mixed at an arbitrary ratio. When it is desired to obtain a copolymer composition having excellent adhesion, the content of the modified hydrogenated copolymer (2) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass. % Or more is recommended. Moreover, when it is desired to obtain a copolymer composition having excellent corrosion resistance, the content of the modified hydrogenated copolymer (2) is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably. It is recommended that it be 10% by weight or less.

Zinc oxide (3) having a core part and a needle-like crystal part used in the present invention has a core part, and has a needle-like crystal part extending from this core part into tetrapods in different four-axis directions. Examples thereof include “Panatetra (registered trademark)” manufactured by Matsushita Electric Industrial Co., Ltd.
By using zinc oxide having a core part and a needle-like crystal part, the number of contact points of zinc oxide in the resin increases, a heat transfer path is easily formed, and the thermal conductivity of the composition is improved. Increasing the amount of zinc oxide (3) having a core part and needle crystal part increases the thermal conductivity of the composition. However, in order to increase the amount of addition, it is necessary to use a styrene-based soft resin. is there.

  In the zinc oxide (3) having the core and the needle crystal part, the diameter of the base part of the needle crystal part is preferably 0.7 to 14 μm, and the length from the base part to the tip of the needle crystal part is 3 to 3 mm. It is preferable that it is 200 micrometers. More preferably, the diameter of the base of the needle-like crystal part is 1 to 14 μm, and the length from the base to the tip of the needle-like crystal part is 10 to 200 μm.

Here, the diameter of the base portion refers to the diameter of the acicular crystal portion at the connecting portion between the core portion and the acicular crystal portion.
The zinc oxide (3) having a core part and a needle-like crystal part used in the present invention is most preferably one in which the needle-like crystal part uniformly extends in four directions in a tetrapod shape, but the needle-like crystal extending from the core part The angle with each acicular crystal portion extending in a direction different from the acicular crystal portion with respect to one of the portions is preferably 90 ° or more and 140 ° or less, more preferably 100 ° or more and 120 ° or less. is there.
Zinc oxide (3) having a core part and a needle-like crystal part can also include zinc oxide surface-treated with a coupling agent in the present invention. The coupling agent used here is a silane coupling agent or a titanate coupling. Agents and aluminum coupling agents are preferably used.
In the copolymer composition of the present invention, acicular zinc oxide may be present. This is because the acicular crystal portion extending in a plurality of directions of the tetrapod-shaped zinc oxide is broken. It does not detract from the main characteristics of the invention.

  Phosphorus flame retardant (4) used in the present invention is a phosphazene compound, phosphate ester, phosphate ester compound such as condensed phosphate ester, phosphinate, phosphate ester amide, phosphorus-containing polymer, phosphine oxide, Tertiary phosphines such as phosphine sulfide, triarylphosphine, trialkylphosphine, bis (diarylphosphino) benzene, and tris (diarylphosphino) benzene are preferably used, and these are used alone or in combination of two or more. It can be used as a mixture.

The copolymer composition of the present invention can impart flame retardancy in consideration of the environment by using a phosphorus flame retardant, and can further suppress discoloration of the resulting copolymer composition when heated.
The phosphorus-based flame retardant (4) suitably used in the present invention may take various forms such as liquid, waxy, solid, etc., depending on the type and structure of the substituents contained. Any shape may be used as long as the effects of the invention are not impaired.
Among the phosphorus-based flame retardants (4) suitably used in the present invention, when it is necessary to consider the heat resistance and low volatility of the phosphorus-based flame retardant (4) itself, phosphazene compounds, bisphenol A and phenol are used. A condensed phosphate ester synthesized as a raw material, a condensed phosphate ester obtained using bisphenol A or resorcin and 2,6-xylenol as raw materials, and a phosphinate are particularly preferably used. Further, when it is necessary to further consider hydrolysis resistance, a phosphazene compound is particularly preferably used.

(4-1) Phosphazene Compound As the phosphazene compound that can be used in the present invention, conventionally known compounds can be widely used. The structure of the phosphazene compound preferably used in the present invention is described in, for example, “Inorganic Polymers” Pretice-Hall International, Inc., 1992, p61-p140, by James E. Mark, Harry R. Allcock, Robert West. .
For example, a cyclic phosphazene compound represented by the following general formula (3) and / or a chain phosphazene compound represented by the following general formula (4) may be mentioned, and among them, a phosphazene compound having these structures is contained in an amount of 95% by weight or more. Those are preferred.

(In the formula, n is an integer of 3 to 25, m is an integer of 3 to 10,000, and the substituent X is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 11 carbon atoms, a fluorine atom, It is a substituent selected from an aryloxy group having a substituent represented by the following general formula (5), a naphthyloxy group, an alkoxy group having 1 to 6 carbon atoms and a substituent represented by an alkoxy-substituted alkoxy group, The hydrogen on the substituent may be partially or entirely substituted with fluorine, and Y in the formula is —N═P (O) (X) or —N = P (X) ₃ , Z represents —P (X) ₄ or —P (O) (X) ₂ )

(In the formula, Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, a phenyl group, or a hetero-element-containing group. Represents a substituent selected from the group consisting of the inside.)

These compounds may be used alone or as a mixture of two or more.
One factor that determines flame retardancy is the concentration of phosphorus atoms contained in the molecule. In the phosphazene compound, the chain phosphazene having a chain structure has a substituent at the molecular end, so that the phosphorus content is lower than that of the cyclic phosphazene compound, and when the same amount is added, the cyclic phosphazene than the chain phosphazene compound. Since the compound is considered to have a higher flame retardancy-imparting effect, the use of a phosphazene compound having a cyclic structure is preferred in the present invention, and a compound containing 95% by weight or more of a cyclic phosphazene compound is preferred.

  The substituent X in the phosphazene compound is not particularly limited, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, tert-butyl group, n-amyl group, Alkyl group such as isoamyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,5-dimethylphenyl Group, aryl group such as 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 4-tertiarybutylphenyl group, 2-methyl-4-tertiarybutylphenyl group, methoxy group, ethoxy group, n- Propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, s-butyloxy group, n-amyloxy group, isoamyloxy group, tert -Alkoxy groups such as amyloxy group, n-hexyloxy group, alkoxy-substituted alkoxy groups such as methoxymethoxy group, methoxyethoxy group, methoxyethoxymethoxy group, methoxyethoxyethoxy group, methoxypropyloxy group, phenoxy group, 2-methylphenoxy Group, 3-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 3,4- Dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,5- Trimethylphenoxy, 3,4,5-trimethylphenoxy, 2-ethylphenoxy, 3-ethyl Ruphenoxy group, 4-ethylphenoxy group, 2,6-diethylphenoxy group, 2,5-diethylphenoxy group, 2,4-diethylphenoxy group, 3,5-diethylphenoxy group, 3,4-diethylphenoxy group, 4-n-propylphenoxy group, 4-isopropylphenoxy group, 4-tertiarybutylphenoxy group, 2-methyl-4-tertiarybutylphenoxy group, 2-phenylphenoxy group, 3-phenylphenoxy group, 4-phenylphenoxy group Examples thereof include alkyl-substituted phenoxy groups, aryl-substituted phenoxy groups, naphthyl groups, naphthyloxy groups, etc., and some or all of these groups may be replaced by groups containing fluorine and / or heteroelements. Absent. Here, the group containing a hetero element is a group containing B, N, O, Si, P, and S atoms. For example, an amino group, an amide group, an aldehyde group, a glycidyl group, a carboxyl group , Groups containing a hydroxyl group, a mercapto group, a silyl group, and the like.

  Further, these compounds may be crosslinked with a crosslinking group selected from the group consisting of a phenylene group, a biphenylene group, and a group (6) shown below by the technique disclosed in International Publication No. WO00 / 09518. .

(Wherein X represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and y represents 0 or 1).
The phosphazene compound having such a crosslinked structure is specifically produced by reacting a dichlorophosphazene oligomer with an alkali metal salt of phenol and an alkali metal salt of an aromatic dihydroxy compound. These alkali metal salts are added to the dichlorophosphazene oligomer slightly in excess of the theoretical amount.
These phosphazene compounds may be used alone or as a mixture of two or more.

The phosphazene compound is a mixture of different structures such as cyclic trimers and cyclic tetramers and chain phosphazenes, but the processability when added to the resin is cyclic trimer and tetramer content. Is higher, specifically, a phosphazene compound containing 80% by weight or more of a cyclic trimer and / or tetramer compound, more preferably 85% by weight or more of a trimer and / or tetramer compound. More preferred is a phosphazene compound containing 93% by weight or more.
Further, when used in combination with a phenolic resin in the present invention, the trimer is preferably 70% by weight or more, more preferably the trimer is 76% by weight or more, still more preferably the trimer is 80% by weight or more, Particularly preferably, when a phosphazene compound containing 85% by weight or more of a trimer is used, a particularly excellent flame retardancy imparting effect can be obtained, and an excellent mechanical property improving effect can be obtained.

The phosphazene compound varies depending on the type and structure of the substituent, but can take various forms such as liquid, waxy, solid, etc., as long as it does not impair the effects of the present invention. Such a shape may be used. If the solid state, preferably a bulk density of 0.45 g / cm ³ or more, more preferably 0.45 g / cm ³ or more, further preferably 0.75 g / cm ³ or less.
The alkali metal components such as sodium and potassium contained in the phosphazene compound are each preferably 200 ppm or less, more preferably 50 ppm or less, and more preferably the total alkali metal component is 50 ppm or less.

  Further, it is desirable that the content of the phosphazene compound in which at least one of the substituents X in the general formula (3) is a hydroxyl group, that is, the phosphazene compound containing a P—OH bond is less than 1% by weight, and chlorine The content is preferably 1000 ppm or less, more preferably 500 ppm or less, and still more preferably 300 ppm or less.

  A phosphazene compound in which at least one of the substituents X is a hydroxyl group may have an oxo-form structure represented by the following general formula (7). Desirably, it is less than% by weight. The same applies to phosphazene compounds having a chain structure represented by the general formula (4).

(In the formula, a + b = n, n is an integer of 3 or more, and X in the formula represents an aryloxy group and / or an alkoxy group which may be the same or different.)

(4-2) Phosphate ester As the phosphate ester suitably used in the present invention, conventionally known ones can be widely used. Examples include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, dixylenyl phenyl phosphate, cresyl dixylenyl phosphate, dicresyl xylenyl phosphate, etc. Is mentioned.
(4-3) Condensed phosphate ester The condensed phosphate ester suitably used in the present invention is, for example, pentaerythritol diphosphate or a phosphate ester compound having the following general formulas (8) and (9).

(Where Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₉ , Q ₁₀ , Q ₁₁ , Q ₁₂ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q ₅ , Q ₆ , Q ₇ , Q ₈ and Q _{13 each} independently represents a hydrogen atom or a methyl group, m 1, m 2, m 3, m 4, m 7, m 8, m 9, m 10 independently represent an integer of 0 to 3; m6 independently represents an integer of 0 to 2, and m11 independently represents an integer of 0 to 4.)

(4-4) Phosphinic Acid Salt The phosphinic acid salt that can be used in the present invention is at least one selected from phosphinic acid salts represented by the following general formula (10) and / or (11) and / or polymers thereof. It is.

(Wherein Q ₁ , Q ₂ , Q ₃ , and Q ₄ represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group, and an aryloxy group, ₅ represents a group selected from alkylene having 1 to 18 carbon atoms, arylalkylene, arylene, alkylarylene, and diarylene, wherein n and m are each an integer of 1 to 3, and x is 1 or 2. M represents a group selected from a metal atom, an amide, an ammonium group, and a melamine derivative after the fourth period of the periodic table, and when x is 2, it may be the same group or a different group.

(4-5) Tertiary phosphines As the tertiary phosphines that can be used in the present invention, conventionally known phosphines can be suitably used, but considering the balance of heat resistance, flame retardancy, and mechanical properties. Then, it is preferable that 10% weight loss temperature when it heats from normal temperature to 600 degreeC with the temperature increase rate of 10 degree-C / min in the inert gas atmosphere by TGA is 150 degreeC-320 degreeC. For example, triarylphosphine, trialkylphosphine, triaryloxyphosphine, trialkoxyphosphine and the like can be mentioned. More specifically, among them, triarylphosphines represented by the following general formula (12) are preferably used.

(Wherein T ₁ , T ₂ , T ₃ , and T ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group, and T ₅ represents a hydrogen atom or a methyl group. M1 , M2, m3, and m4 each independently represents an integer of 0 to 5, m5 independently represents an integer of 0 to 4. Further, n in the formula represents an integer of 0 to 3. A naphthyl group can also be suitably used as the aryl group, and all three aryl groups on the phosphorus atom may be the same group or different groups.

The phosphorus content contained in the phosphorus-based flame retardant (4) suitably used in the present invention is preferably 8 to 25% by mass, more preferably, when considering flame retardancy and discoloration during heating residence. It is 9-20 mass%, More preferably, it is 10-15 mass.
The water content contained in the phosphorus-based flame retardant (4) suitably used in the present invention is preferably 1000 ppm or less, more preferably 800 ppm or less, and even more preferably 650 ppm, considering electrical characteristics, hydrolysis resistance, and the like. Hereinafter, it is further 500 ppm or less, more preferably 300 ppm or less, and the acid value measured based on JIS K6751 is preferably 1.0 or less, more preferably 0.5 or less.

In addition, the phosphorus-based flame retardant (4) preferably used in the present invention has solubility in water (mixed sample with distilled water at a concentration of 0.1 g / mL) from the viewpoint of hydrolysis resistance and moisture absorption resistance. The amount of the sample dissolved in water after stirring for 1 hour at room temperature) is preferably 100 ppm or less, more preferably 50 ppm, and still more preferably 25 ppm or less.
The phosphorus-based flame retardant (4) of the present invention is 600 to 600 ° C. at a heating rate of 10 ° C./min in an inert gas atmosphere by TGA in consideration of flame retardancy, low smoke generation during combustion, low volatility, and the like. The difference between the temperature when the weight is reduced by 50% by weight and the temperature when the weight is decreased by 5% by weight when heated to 0 ° C. is preferably 20 to 150 ° C., more preferably 20 to 120 ° C.
Moreover, when it uses with respect to the resin, when the flame retardance efficiency by the carbonization layer formation promotion effect at the time of combustion is considered, the thing at the time of the weight reduction of 50 weight% is 320-500 degreeC, More preferably, it is 350 ~ 460 ° C.

The paraffinic oil (5) used in the present invention is a base oil obtained by hydrogenating a petroleum fraction or residual oil and refining it or by decomposing it. Oil that occupies 50% or more. Thermal conductivity of copolymer composition and resin sheet obtained by high filling and melt-kneading of zinc oxide (3) having needle-like crystal parts when producing melt-kneaded copolymer composition and resin sheet Used for improvement and flexibility.
The kinematic viscosity at 40 ° C. of the paraffinic oil (5) used in the present invention is preferably 100 mm ² / sec or more, more preferably 100 to 10,000 mm ² / sec, still more preferably 200 to 5000 mm ² / sec.
As the paraffinic oil (5) used in the present invention, for example, NA Solvent manufactured by Nippon Oil & Fats Co., Ltd., “Diana (registered trademark) Process Oil PW-90, PW-380” manufactured by Idemitsu Kosan Co., Ltd., Idemitsu Petrochemical Co., Ltd. Examples thereof include IP-solvent 2835 manufactured by Sanko Chemical Co., Ltd. and “Neothiozole (trademark)”.

  In addition to the paraffinic oil (5) used in the present invention, for the purpose of imparting flexibility, a naphthenic oil having a naphthenic ring carbon number of 30 to 45%, an aromatic oil having an aromatic carbon number exceeding 30%, and a castor oil , Linseed oil, polybutene, low molecular weight polybutadiene, liquid paraffin, and the like can be used in amounts that do not impair the object of the present invention.

  In the copolymer composition of the present invention, a styrenic soft resin comprising a hydrogenated copolymer (1) and / or a modified hydrogenated copolymer (2), a core and an extension from the core in different four axial directions. The blending ratio of zinc oxide (3) having a needle-like crystal part, phosphorus flame retardant (4), and paraffinic oil (5) is determined depending on the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer. For the total amount of 100% by mass of the styrene-based soft resin composed of the coalescence (2), the zinc oxide (3) having a needle crystal part, the phosphorus-based flame retardant (4), and the paraffinic oil (5), The total content of the styrenic soft resin comprising the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2) and the paraffinic oil (5) is 5 to 85% by mass, and the paraffin Ratio obtained by dividing the mass of oil based oil (5) by the mass of styrene resin 1 is 0 <r1 ≦ 2, the amount of zinc oxide (3) having needle-like crystal parts is 10 to 90% by mass, and the amount of phosphorus flame retardant (4) is 5 to 40% by mass. The copolymer composition obtained is excellent in thermal conductivity, heat resistance, flexibility, flame retardancy, and discoloration resistance during heat processing.

In the copolymer composition of the present invention, a copolymer composition comprising a styrene-based soft resin, zinc oxide (3) having a needle-like crystal part, a phosphorus-based flame retardant (4), and a paraffinic oil (5). The blending ratio of the total amount of the styrenic soft resin and the paraffinic oil (5) with respect to the total total amount of 100% by mass is 5 to 85% by mass, preferably 10 from the viewpoints of thermal conductivity, heat resistance, and flexibility. It is -60 mass%, More preferably, it is 15-50 mass%.
In the copolymer composition of the present invention, the total amount of the styrenic soft resin comprising the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2) is used as the denominator, and the paraffinic oil (5) is used. The mass ratio r1 in the case of a molecule is 0 <r1 <2, preferably 0.2 <r1 <1.8, more preferably 0, from the viewpoints of flexibility, flame retardancy, and bleedout prevention. .5 <r1 <1.5.

Styrenic soft resin comprising hydrogenated copolymer (1) and / or modified hydrogenated copolymer (2), zinc oxide (3) having needle-like crystal parts, phosphorus flame retardant (4), and paraffin The content of zinc oxide (3) having needle-like crystal parts with respect to 100% by mass of the total amount of the copolymer composition comprising the oil (5) is from the viewpoint of thermal conductivity, flexibility, and flame retardancy. 10 to 90% by mass, preferably 30 to 90% by mass, more preferably 51 to 90% by mass, still more preferably 65 to 90% by mass, and particularly preferably 78 to 90% by mass. It is.
In particular, by setting the content of zinc oxide (3) having a core part and a needle-like crystal part to 65 to 90% by mass, surprisingly, the thermal conductivity in the composition is remarkably increased and the heat dissipation is remarkably improved. Nevertheless, the composition is preferred because the flexibility of the composition is maintained and the composition is more balanced.

Zinc oxide (3) having a core part and a needle-like crystal part has a lower bulk density and a higher bulk compared to amorphous particulate zinc oxide, so when a thermoplastic resin other than a styrene-based soft resin is used, In some cases, the zinc oxide content of 65% by mass or more cannot be obtained. However, when a styrenic soft resin is used, a zinc oxide-containing composition of 65% by mass or more can be surprisingly made and flexible. It is preferable because the property can be maintained.
Styrenic soft resin comprising hydrogenated copolymer (1) and / or modified hydrogenated copolymer (2), zinc oxide (3) having needle-like crystal parts, phosphorus flame retardant (4), and paraffin The content of the phosphorus-based flame retardant (4) with respect to 100% by mass of the total amount of the copolymer composition comprising the oil (5) is 5 to 40% by mass from the viewpoint of flame retardancy and mechanical strength. The content is preferably 5 to 30% by mass, more preferably 5 to 25% by mass.
When the content of the phosphorus flame retardant (4) is less than 5% by mass, sufficient flame retardancy may not be obtained, which is not preferable. Moreover, when it exceeds 40 mass%, the mechanical strength of a composition falls.

In the copolymer composition of the present invention, the total amount of the styrene soft resin and the paraffinic oil (5) comprising the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2) is used as the denominator. The mass ratio r2 when the phosphorus-based flame retardant (4) is a molecule is preferably 0.1 <r2 <2, more preferably 0 from the viewpoints of flexibility, flame retardancy, and prevention of flame retardant bleed out. 0.2 <r2 <1.8, more preferably 0.3 <r2 <1.6, and particularly preferably 0.4 <r2 <1.4.
In order to obtain a composition having good fluidity, the ratio r2 of the phosphorus-based flame retardant (4) is preferably 0.9 <r2 <2, more preferably 0.9 <r2 <1.8, and further preferably Is 0.9 <r2 <1.6, particularly preferably 0.9 <r2 <1.4.
In order to obtain a composition excellent in strength at bending and elongation at heat-melting, the ratio r2 of the phosphorus-based flame retardant (4) is preferably 0.1 <r2 <0.9, more preferably Is 0.2 <r2 <0.9, more preferably 0.3 <r2 <0.9, and particularly preferably 0.4 <r2 <0.9.

In the copolymer composition of the present invention, a styrene-based soft resin comprising a hydrogenated copolymer (1) and / or a modified hydrogenated copolymer (2), zinc oxide having a core and a needle crystal part (3 ), Phosphorus-based flame retardant (4), paraffinic oil (5), and 10-400 W / m · k heat conductive filler (6) other than zinc oxide (3) having needle-like crystal parts are added. May be.
The thermally conductive filler (6) is a filler having a thermal conductivity in the range of 10 to 400 W / m · K other than zinc oxide (3) having a core part and a needle crystal part, for example, Examples thereof include metal powder, metal nitride, metal carbide, and metal oxide.
Examples of the metal powder include gold, silver, copper, and aluminum.
Examples of the metal nitride include boron nitride, silicon nitride, and aluminum nitride.
Examples of the metal carbide include silicon carbide.
Examples of the metal oxide include zinc oxide, aluminum oxide, and magnesium oxide.

Moreover, the shape of these heat conductive fillers may be fibrous and / or non-fibrous (plate-like, scale-like, granular, irregular shape, spherical).
Among these, from the workability and heat transfer rate improving effect when added to the copolymer composition of the present invention, preferably a metal oxide, a metal nitride, more preferably a metal nitride, still more preferably. Boron nitride.
When the thermal conductivity of the thermally conductive filler is 10 to 400 W / m · K, when it is added to the copolymer composition of the present invention, a sufficient effect of improving the thermal conductivity is obtained.

  When zinc oxide (3) having acicular crystal parts used in the present invention and 10 to 400 W / m · k heat conductive filler (6) other than zinc oxide (3) having acicular crystal parts are used in combination The blending ratio of the styrene-based soft resin comprising the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2), zinc oxide (3) having a needle-like crystal part, phosphorus-based flame retardant (4 ), Paraffinic oil (5), and the total amount of the copolymer composition comprising 10 to 400 W / m · k of the thermally conductive filler (6) other than zinc oxide (3) having needle-like crystal parts. The total content of zinc oxide (3) having a needle-like crystal part and the thermally conductive filler (6) is preferably 100% by mass from the viewpoints of thermal conductivity, flexibility, and flame retardancy. Is 10 to 90 mass%, more preferably 30 to 90 mass%, still more preferably 51 It was 90 wt%, and most preferably from 65 to 90 wt%, especially preferably from 78 to 90 wt%.

The mass ratio r3 of the zinc oxide (3) having needle-like crystal parts and the thermally conductive filler (6) is determined by using the zinc oxide (3) having needle-like crystal parts as a denominator and the heat conductive filler (6 ) Is a molecule, the mass ratio r3 is preferably 0 <r3 ≦ 1, more preferably 0 <r3 <0.8, from the viewpoints of thermal conductivity, flexibility, and flame retardancy. Preferably 0 <r3 ≦ 0.5.
Zinc oxide (3) phosphorus flame retardant having a core part and a needle-like crystal part in a styrene-based soft resin comprising the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2) of the present invention (4) A copolymer composition comprising a paraffinic oil (5) and a heat conductive filler (6) other than zinc oxide is a metal hydroxide flame retardant (7) other than the phosphorus flame retardant (4). ) May be included.

Examples of the metal hydroxide flame retardant (7) include magnesium hydroxide and aluminum hydroxide. These metal hydroxides that have been surface-treated by fatty acid treatment, nitric acid compound treatment, silane coupling agent treatment, titanate coupling agent treatment, etc. are also preferably used. Of the metal hydroxide flame retardants, aluminum hydroxide is preferred from the viewpoint of thermal conductivity.
The average particle diameter of the metal hydroxide-based flame retardant (7) is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm from the viewpoints of mechanical strength and thermal conductivity.
Examples of the metal hydroxide flame retardant (7) used in the present invention include “Pyrolyzer (registered trademark) HG” manufactured by Ishizuka Glass Co., Ltd.

When the phosphorus-based flame retardant (4) and the metal hydroxide-based flame retardant (7) used in the present invention are used in combination, the blending ratio is as follows: hydrogenated copolymer (1) and / or modified hydrogenated copolymer (2 ), A zinc oxide (3) having a needle crystal part, a phosphorus flame retardant (4), a paraffinic oil (5), a heat conductive filler (6) other than zinc oxide, and metallic water The total content of the phosphorus-based flame retardant (4) and the metal hydroxide-based flame retardant (7) is 100% by mass based on the total amount of the copolymer composition composed of the oxide-based flame retardant (7). From the viewpoint of flame retardancy and mechanical strength, 5 to 40% by mass is preferable, 5 to 30% by mass is more preferable, and 5 to 25% by mass is more preferable.
In addition, the mass ratio r4 of the phosphorus-based flame retardant (4) and the metal hydroxide-based flame retardant (7) has the phosphorus-based flame retardant (4) as a denominator and the metal hydroxide-based flame retardant (7) as a numerator. In this case, the mass ratio r4 is preferably 0 <r4 ≦ 2, more preferably 0 <r4 ≦ 1, more preferably, from the viewpoints of flexibility, flame retardancy, and resistance to discoloration during heat retention. 0 <r4 ≦ 0.5.

The copolymer composition of the present invention is an acrylic resin, a fatty acid, a fatty acid salt, an anti-drip agent that is a flame retardant aid, an antioxidant, and an ultraviolet absorber as long as the object of the present invention is not impaired. Additives such as fillers, heat stabilizers, antistatic agents, light stabilizers, anti-aging agents, and coloring agents can be blended.
The acrylic resin that may be used in the present invention is specifically a polymer or copolymer of at least one compound selected from the group consisting of (meth) acrylic acid alkyl esters. Examples of the (meth) acrylic acid alkyl ester include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and dodecyl methacrylate. Any of these compounds can be used as long as it is a copolymer obtained by polymerizing these compounds alone or in combination of two or more kinds, and acrylic rubber particles obtained by polymerizing alkyl acrylate esters ( A graft copolymer obtained using a (meth) acrylic acid alkyl ester as a main component can also be used, and examples thereof include “Hybrene (trademark)” manufactured by Zeon Kasei Co., Ltd.

The blending ratio of the acrylic resin is preferably 5% by mass or less, more preferably 0.01 to 5% by mass, and further preferably 0.05 to 2% by mass with respect to 100% by mass of the copolymer composition.
The fatty acid and fatty acid salt that may be used in the present invention may be a saturated or unsaturated fatty acid and fatty acid salt, more preferably 8 to 34 carbon atoms, and more preferably 14 to 22 carbon atoms. Saturated fatty acids and fatty acid salts are more preferable. Specifically, fatty acids such as lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, oleic acid, capric acid, behenic acid, linoleic acid, and magnesium salts of these fatty acids, In addition to alkaline earth metal salts such as calcium salts and barium salts, mention may be made of zinc metal salts, among which stearic acid, oleic acid, lauric acid and their alkaline earth metal salts (magnesium salt, calcium salt) ), Zinc metal salts are preferably used.

The blending ratio of the fatty acid and / or fatty acid salt is preferably 5% by mass or less, more preferably 0.01 to 5% by mass, and still more preferably 0.05 to 2% by mass with respect to 100% by mass of the copolymer composition. .
The anti-drip agent that may be used in the present invention is a flame retardant aid that suppresses drip at the time of combustion. Specific examples thereof include polytetrafluoroethylene, and the molecular weight of polytetrafluoroethylene is 100,000 or more are preferable, and 200,000 to 3,000,000 are more preferable. For example, “Metablene (registered trademark)” manufactured by Mitsubishi Rayon Co., Ltd. may be used.
Antioxidants that may be used in the present invention include hindered phenolic antioxidants, amine-based and hydroxylamine-based antioxidants. Examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] and pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate].

Examples of ultraviolet absorbers that may be used in the present invention include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and nickel complex ultraviolet absorbers. Particularly preferred are benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers.
These additives may be added at the time of kneading, or may be included in the copolymer in advance during the production of the hydrogenated copolymer or the modified hydrogenated copolymer.
The copolymer composition of the present invention can be easily produced by a Brabender, kneader, Banbury mixer, twin-screw or single-screw extruder, etc. as a method for producing the above composition. Molding can be performed by a molding method such as injection molding, injection press molding, or gas injection molding.

Further, as a molding method for obtaining the copolymer composition as a sheet, it is kneaded by the above method and then molded by extrusion sheet molding, T-die sheet molding, calendar molding, roll molding, press molding, inflation molding or the like. be able to.
The copolymer composition of the present invention is a thermoplastic and heat-plasticized melt can be easily cast into a continuous thin sheet by calender roll or T-die sheet molding, and the sheet molded product has flexibility. It is suitably used as a resin sheet because it is obtained as a scroll for holding and has little discoloration during heat retention.

The thickness of the resin sheet of the present invention is preferably 30 μm to 30 mm. In a case where the heat conductivity is required to quickly dissipate the heat from the heating element, a thin sheet having a short heat conduction path is preferable, and the sheet thickness is more preferably 30 μm to 3 mm, more preferably 30 μm to 1 mm is more preferable. Further, in the case of a spacer application where a distance between a heat generating body such as a CPU and a heat radiating body such as a heat sink is used, a thick sheet is preferable, and specifically, the sheet thickness is more preferably 1 mm to 30 mm.
Moreover, it is preferable that the surface of a resin sheet is smooth, and it is preferable that the value of the 60 degree surface gloss in the resin sheet surface measured based on JIS * K-7105 is 10 or more.
The copolymer composition of the present invention is thermoplastic and is easy to mold by injecting a heat-plasticized melt into a mold, and the composition itself has excellent thermal conductivity, and the composition Since it itself is flame retardant, it is suitably used as a flame-retardant heat-dissipating molded article.
The equivalent thermal conductivity of the flame-retardant heat dissipation molded article is preferably 0.7 to 10 W / m · K, more preferably 1.0 to 8.0 W / m · K.

The flame-retardant heat-dissipating molded article having such characteristics can be obtained by heating and plasticizing the composition of the present invention.
In the flame-retardant heat dissipation molded object, a flame-retardant heat dissipation sheet is preferable.
The thickness of the flame retardant heat dissipation sheet is preferably a thin sheet having a short heat conduction path in a case where heat from the heating element is required to be quickly dissipated, and more specifically, a sheet thickness of 30 μm to 3 mm is more preferable. 30 μm to 1 mm is more preferable.
The heat-dissipating molded body is a heat-dissipating part for computers such as personal computers and home-use game machines, a heat-dissipating part for DVD players and DVD recorders, a heat-dissipating part for HDD recorders, a home TV, plasma display, and liquid crystal TV High heat conductivity is required, such as heat dissipation parts used for mobile phone, various computers, various AV equipment, OA equipment, car stereo, car navigation system, inverter, lighting, automotive electrical components It is preferably used for the intended use.

Specifically, it is suitably used for power transistors for power supplies, heat dissipation caps for power modules, heat dissipation tubes, heat dissipation molds for temperature sensors, heat dissipation insulation mold products for halogen lamp transformers, and the like.
Examples of applications of heat dissipation sheets include heat dissipation sheets that connect semiconductor components such as CPUs and graphic chips of computers such as personal computers and home-use game machines with heat dissipation components such as heat sinks, and heat dissipation sheets that dissipate heat from semiconductor components. It is suitably used for applications that require conductivity.
Hereinafter, the present invention will be described based on examples.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples. A hydrogenated copolymer and the like were obtained by the following procedure. In addition, the characteristics and physical properties of the polymer were measured as follows.
1. Characteristics of hydrogenated copolymer and the like 1) Content of vinyl aromatic unit: Measured using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450).
2) Content of polymer block composed of vinyl aromatic: M. Kolthoff, etal. , J .; Polym. Sc i. 1, 429 (1946).
3) Amount of vinyl bonds and hydrogenation rate: Measured using a nuclear magnetic resonance apparatus (manufactured by BRUKER, DPX-400).
4) Molecular weight and molecular weight distribution: Measured by GPC [device is manufactured by Waters], tetrahydrofuran was used as a solvent, and measurement conditions were performed at a temperature of 35 ° C. The molecular weight is a weight average molecular weight obtained by using a calibration curve (created using the peak molecular weight of standard polystyrene) obtained by measuring the molecular weight of the peak of the chromatogram from measurement of commercially available standard polystyrene. The molecular weight when there are a plurality of peaks in the chromatogram refers to the average molecular weight determined from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram). The molecular weight distribution is a ratio of the obtained weight average molecular weight and number average molecular weight.

5) Crystallization peak and crystallization peak calorie: Measured by DSC [manufactured by Mac Science, DSC3200S]. The temperature was increased from room temperature to 150 ° C. at a rate of temperature increase of 30 ° C./min, and then the temperature was decreased to −100 ° C. at a rate of temperature decrease of 10 ° C./min to determine the presence or absence of a crystallization peak. Further, when there was a crystallization peak, the temperature at which the peak appeared was defined as the crystallization peak temperature, and the crystallization peak calorie was measured.
6) Modification rate: Applying the property that the modified component is adsorbed to a GPC column with a silica gel as a filler, the above-mentioned polystyrene gel (Showa Denko) Both chromatograms of GPC (manufactured by Shodex Co., Ltd.) and silica column GPC (Zorbax manufactured by DuPont) were measured, and the amount of adsorption on the silica column was measured from the difference between them to determine the modification rate.

<Preparation of hydrogenated copolymer (1) and modified hydrogenated copolymer (2)>
Preparation of hydrogenated copolymer and the like Hydrogenated copolymer and the like were prepared by the following method. In the following examples, the hydrogenation catalyst used for the hydrogenation reaction was prepared by the following method.
<Adjustment of hydrogenation catalyst>
Charge 1 liter of dried and purified cyclohexane to a nitrogen-substituted reaction vessel, add 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride, and stir the n-hexane solution containing 200 mmol of trimethylaluminum with sufficient stirring. The mixture was added and allowed to react at room temperature for about 3 days.

<Preparation of hydrogenated copolymer (1)>
Preparation of the hydrogenated copolymer (1) (referred to as polymer 1) was carried out by the following method using a stirrer having an internal volume of 10 L and a jacketed tank reactor.
After charging 10 parts by mass of cyclohexane into the reactor and adjusting the temperature to 70 ° C., n-butyllithium was 0.076% by mass with respect to the weight of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor), 0.4 mol of N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 1 mol of n-butyllithium, and then a cyclohexane solution containing 8 parts by mass of styrene as a monomer (monomer concentration 22 Mass%) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the internal temperature of the reactor to 70 ° C.

Next, a cyclohexane solution (monomer concentration of 22% by mass) containing 48 parts by mass of butadiene and 36 parts by mass of styrene was continuously supplied to the reactor at a constant rate over 60 minutes, and then reacted for 30 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C. When the polymer solution sampled immediately after the supply was analyzed, the polymerization conversion of butadiene: 90%, the polymerization conversion of styrene: 100%, and the styrene content in the polymer was 47.8% by mass (Block B Styrene content is 42.9% by mass).
Thereafter, a cyclohexane solution containing 8 parts by mass of styrene as a monomer (monomer concentration: 22% by mass) is added over about 3 minutes, and the reaction is carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C. Got. The vinyl aromatic content of the obtained copolymer is 52% by mass, the content of the polymer block made of vinyl aromatic is 16% by mass, the vinyl bond content of the butadiene part is 21% by mass, and the weight average molecular weight. Was 165,000 and the molecular weight distribution was 1.2.

  Next, 100 mass ppm of the above hydrogenation catalyst as titanium with respect to the weight of the copolymer was added to the obtained copolymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. After completion of the reaction, methanol is added, and then octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer is added in an amount of 0.3% by weight based on the weight of the polymer. A hydrogenated copolymer (hereinafter referred to as polymer 1) was obtained. The hydrogenation rate of polymer 1 was 99%. As a result of dynamic viscoelasticity measurement, the peak temperature of tan δ was at −15 ° C. As a result of DSC measurement, there was no crystallization peak.

  Adjustment of the hydrogenated copolymer (1) (referred to as polymer 2) is as follows. First stage: 4.5 parts by mass of styrene, second stage: 49 parts by mass of butadiene and 42 parts by mass of styrene, third stage: styrene 4. Using 5 parts by mass, a copolymer was obtained in the same manner as in Polymer 1. The content of the vinyl aromatic unit in the obtained copolymer was 51% by mass, the content of the polymer block composed of vinyl aromatic was 9% by mass, the amount of vinyl bonds in the butadiene portion was 21% by mass, and the weight average The molecular weight was 175,000 and the molecular weight distribution was 1.2. Next, hydrogenation was carried out in the same manner as in polymer 1 to obtain a hydrogenated copolymer (hereinafter referred to as polymer 2). The hydrogenation rate of polymer 2 was 99%. As a result of dynamic viscoelasticity measurement, the peak temperature of tan δ was at −14 ° C. As a result of DSC measurement, there was no crystallization peak.

<Preparation of Modified Hydrogenated Copolymer (2)>
The modified hydrogenated copolymer (2) (referred to as polymer 3) was prepared by using tetraglycidyl-1,3-bisaminomethylcyclohexane (hereinafter referred to as a modifier) as a modifier in the living polymer solution from the second group. M1) was used for the polymerization. A modified copolymer was obtained in the same manner as in Polymer 1 except that the reaction was equimolar with n-butyllithium. The content of the vinyl aromatic unit in the resulting modified copolymer is 52% by mass, the content of the polymer block made of vinyl aromatic is 16% by mass, the amount of vinyl bonds in the butadiene portion is 21% by mass, and weight. The average molecular weight was 165,000 and the molecular weight distribution was 1.2.

  Next, like the polymer 1, the hydrogenation catalyst was added to the modified copolymer at 100 ppm by weight as titanium with respect to the weight of the copolymer, and the hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Went. After completion of the reaction, methanol is added, and then octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer is added in an amount of 0.3% by weight based on the weight of the polymer. A modified hydrogenated copolymer (hereinafter referred to as polymer 3) was obtained. The hydrogenation rate of polymer 3 was 99%. As a result of dynamic viscoelasticity measurement, the peak temperature of tan δ was -15 ° C. As a result of DSC measurement, there was no crystallization peak.

<Zinc oxide (3)>
Zinc oxide (3) having a core part and a needle-like crystal part is not subjected to surface treatment. Zinc oxide having needle-like crystals extending in different four-axis directions from the core part and the core part, manufactured by Amtec Corporation, “ Panatetra (registered trademark), WZ-0501 "(the diameter of the base of the needle-like crystal part is 0.7 to 14 μm, the length from the base to the tip of the needle-like crystal part is 3 to 200 μm, and zinc oxide (3) ) Was used.
<Phosphorus flame retardant (4)>
As the phosphorus flame retardant (4), “SPS-100” (referred to as phosphorus flame retardant 4-1) manufactured by Otsuka Chemical Co., Ltd., which is a phosphazene compound, was used.
In addition, “TPP (trade name)” (substance name: triphenyl phosphate) (referred to as phosphorus flame retardant 4-2) manufactured by Daihachi Chemical Co., Ltd., which is a phosphate ester compound, was used.

<Paraffin oil (5)>
As the paraffinic oil, “Diana (registered trademark) process oil PW380 (40 ° C. kinematic viscosity 382 mm ² / sec, paraffinic oil (5))” manufactured by Idemitsu Kosan Co., Ltd. was used.
<Thermal conductive filler (6)>
As the heat conductive filler (6), “SHOBYN (registered trademark) UHP (registered trademark) -1” (average particle size 10 μm, thermal conductivity of about 130 W / m · K, manufactured by Showa Denko KK, which is boron nitride. Thermally conductive filler 6-1) was used.
Further, “high purity silicon nitride powder SN-E03 (trademark)” manufactured by Ube Industries, Ltd., which is silicon nitride (average particle size 1.0 μm, thermal conductivity of about 80 W / m · K, thermal conductive filler 6-2 Was used).
Moreover, “Shapal (registered trademark) E-grade” manufactured by Tokuyama Co., Ltd., which is aluminum nitride (average particle size 1.1 μm, thermal conductivity about 200 W / m · K, thermal conductive filler 6-3) Was used.

<Metal hydroxylated flame retardant (7)>
“Pyrolyzer (registered trademark) HG” (referred to as metal hydroxide flame retardant (7)) manufactured by Ishizuka Glass Co., Ltd. was used as the metal hydroxide.
The evaluation is performed according to the following items.
<Hardness>
The hardness of a 1 mm (120 mm long × 120 mm wide) press sheet was measured by a method according to JIS K6301 using an A type hardness meter.

<Thermal conductivity>
Using a 1 mm thick (120 mm long x 120 mm wide) press sheet, a rapid thermal conductivity measuring device QTM-500 (thin wire heating method) equipped with a thin film measurement software (SOFT-QTM5W) manufactured by Kyoto Electronics Industry Co., Ltd. The thermal conductivity was measured. Measurement is a method of obtaining thermal conductivity with a box type probe (PD-11) using a reference plate (foamed polyethylene, silicon rubber, quartz glass) whose thermal conductivity is known (described in Japanese Patent Publication No. 5-12361) ) To obtain the thermal conductivity of the resin sheet.
<Flame retardance>
Using a 1 mm thick (120 mm long × 120 mm wide) press sheet, based on the UL-94 vertical combustion test, 5 test pieces were contacted twice for a total of 10 times, and the total number of seconds for combustion and the presence or absence of dripping were confirmed. did.

<Yellowness measurement>
The copolymer composition pellets were put into an injection molding machine EC60 manufactured by Toshiba Machine, and an injection molded piece of 2 mm × 40 mm × 70 mm was molded at a cylinder temperature of 200 ° C. and a mold temperature of 30 ° C. The yellowness of the molded piece molded immediately after plasticization in the cylinder and the molded piece molded by retaining for 60 minutes after plasticization was measured.

The measurement is based on JIS T7105 (Plastic optical characteristics test method) using MSC-5N-GV5 (equipment under JISZ8722-C conditions) using Suga Test Instruments Co., Ltd. Was used to measure the yellowing degree ΔYI.
Yellowing degree ΔYI = YI−YI0
ΔYI: yellowing degree
YI: Yellowness of the molded piece molded after staying for 60 minutes
YI0: Yellowness of the molded product molded immediately after plasticization

<Measurement of equivalent thermal conductivity>
The thermal resistance R at a measurement temperature of 30 ° C. was determined using a Hitachi, Ltd. resin material thermal resistance measuring device, PMFA038-1. The measurement was performed by a steady method according to ASTM D5470. From the obtained thermal resistance R, the equivalent thermal conductivity was calculated using the following equation.
Equivalent thermal conductivity (W / m · k) = L / (R × A)
L: Sample thickness (m)
R: Thermal resistance value (° C / W)
A: Sample cross-sectional area (m ² )

[Examples 1-8 and Comparative Examples 1-3]
Each component of the polymers 1 to 3 obtained above, paraffinic oil, zinc oxide, phosphorus flame retardant, metal hydroxide flame retardant, and heat conductive filler is blended as shown in Table 1, with the cylinder temperature Melt-kneading was performed in a twin-screw extruder (PCM30 30 mmφ, L / D = 33, total length of the heated portion 999 mm, manufactured by Ikegai Steel Co., Ltd.) set at 200 ° C. and a screw rotation speed of 200 rpm to obtain a copolymer composition. It was.
A test piece was obtained as a resin sheet having a thickness of 1 mm and a length of 120 mm and a width of 120 mm by press molding the obtained copolymer composition heated at 150 ° C.
The results are shown in Table 1.
Moreover, the copolymer composition obtained by the said compounding composition obtained the sheet | seat of width 50mm and thickness 1mm with the single screw extruder which attached the die | dye to the front-end | tip at the extruder front-end | tip. The obtained heat-dissipating sheet was cut to obtain a test piece having a thickness of 1 mm, a length of 10 mm, and a width of 10 mm, and the equivalent thermal conductivity was measured. The results are shown in Table 1.

  The copolymer composition in the present invention, the resin sheet obtained by molding this, and the molded product for heat dissipation are excellent in thermal conductivity, have few volatile components by heating, and are excellent in flexibility. Heat dissipation parts for computers such as game consoles, heat dissipation parts for DVD players and DVD recorders, heat dissipation parts for HDD recorders, heat dissipation parts such as display power supply units for home TVs, plasma displays, liquid crystal TVs, mobile phones, various types Suitable for applications that require high thermal conductivity, such as heat-dissipating parts used in computers, various AV equipment, OA equipment, car stereos, car navigation systems, inverters, lighting, and automotive electrical components for air conditioners. Used for.

Claims (14)

Hydrogenated copolymer (1) satisfying the following (a) to (d) by adding hydrogen to a copolymer comprising a conjugated diene and a vinyl aromatic and / or a copolymer comprising a conjugated diene and a vinyl aromatic A styrenic soft resin comprising a modified hydrogenated copolymer (2) satisfying the following (a) to (d) in which hydrogen is added to and at least one atomic group having at least one functional group is bonded: And zinc oxide (3) having needle-like crystal parts extending in different four-axis directions from the core part, phosphorus flame retardant (4), and paraffin oil (5). ) To (D) are satisfied.
(A) The content of vinyl aromatic units is more than 50% by mass and 90% by mass or less.
(B) The amount of the polymer block made of vinyl aromatic is 40% by mass or less.
(C) The weight average molecular weight is 50,000 to 1,000,000.
(D) The hydrogenation rate of the double bond based on the conjugated diene is 10% or more.
(1) + (2) + (3) + (4) + (5) = 100 mass%,
(A) (1) + (2) + (5) = 5-85 mass%
(B) 0 <(5) / [(1) + (2)] ≦ 2 (mass ratio)
(C) (3) = 10 to 90% by mass
(D) (4) = 5-40% by mass   The modified hydrogenated copolymer (2) is characterized in that at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. The copolymer composition according to claim 1.   The copolymer according to claim 1 or 2, wherein the amount of the polymer block composed of vinyl aromatic in the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2) is less than 10% by mass. Composition.   The copolymer according to claim 1 or 2, wherein the amount of the polymer block composed of vinyl aromatic in the hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2) is 10 to 40% by mass. Combined composition. The hydrogenated copolymer (1) and / or the modified hydrogenated copolymer (2) is a hydrogenated product of a copolymer having at least one structure selected from the following general formula. The copolymer composition according to item 1.
(I) B
(B) B-A
(C) B-A-B
(D) (B-A) _m -X
(E) (B-A) _n- X-A _p
(Here, B is a random copolymer block of conjugated diene and vinyl aromatic, A is a vinyl aromatic polymer block, m is an integer of 2 or more, and n and p are each 1 or more. (It is an integer. X represents a coupling agent residue.) The modified hydrogenated copolymer (2) has at least one atomic group having at least one functional group selected from the following formula bonded thereto. A copolymer composition.

(In the above formula, R ^{1 to} R ⁴ are hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. 24 hydrocarbon groups.
R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. In the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , elements such as oxygen, nitrogen, and silicon are bonded in a bonding mode other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group. May be. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms. )   A modified hydrogenated copolymer (2) is obtained by adding a functional group-containing modifier to the living terminal of a copolymer of a conjugated diene and a vinyl aromatic obtained using an organolithium compound as a polymerization catalyst. The copolymer composition according to any one of claims 1 to 6, wherein the copolymer is hydrogenated. Hydrogenated copolymer (1) and / or modified hydrogenated copolymer (2), zinc oxide having needle-like crystal part (3), phosphorus flame retardant (4), paraffinic oil (5), And containing a heat conductive filler (6) of 10 to 400 W / mK other than zinc oxide (3) having needle-like crystal parts, and satisfying the following (A) to (E): The copolymer composition of any one of -7.
(1) + (2) + (3) + (4) + (5) + (6) = 100 mass%,
(A) (1) + (2) + (5) = 5-85 mass%
(B) 0 <(5) / [(1) + (2)] ≦ 2 (mass ratio)
(C) (3) + (6) = 10 to 90% by mass
(D) 0 <(6) / (3) ≦ 1
(E) (4) = 5-40% by mass Hydrogenated copolymer (1) and / or modified hydrogenated copolymer (2), zinc oxide (3) having acicular crystal parts, phosphorus flame retardant (4), paraffinic oil (5), acicular The heat conductive filler (6) other than zinc oxide (3) having a crystal part further contains a metal hydroxide flame retardant (7), and satisfies the following (A) to (F): The copolymer composition according to claim 8.
(1) + (2) + (3) + (4) + (5) + (6) + (7) = 100 mass%,
(A) (1) + (2) + (5) = 5-85 mass%
(B) 0 <(5) / [(1) + (2)] ≦ 2 (mass ratio)
(C) (3) + (6) = 10 to 90% by mass
(D) 0 <(6) / (3) ≦ 1
(E) (4) + (7) = 5-40% by mass
(F) 0 <(7) / (4) ≦ 2   The copolymer composition according to claim 8 or 9, wherein the thermally conductive filler (6) is at least one selected from silicon nitride, aluminum nitride, silicon carbide, and boron nitride.   11. The copolymer composition according to claim 1, wherein the phosphorus content of the phosphorus-based flame retardant (4) is 8 to 25% by mass.   The copolymer composition according to any one of claims 1 to 11, wherein the phosphorus-based flame retardant (4) is phosphazene.   The resin sheet which consists of a copolymer composition of any one of Claims 1-12.   Use of the copolymer composition according to any one of claims 1 to 12 for a flame-retardant heat dissipation molded article.