JP3112519B2 - Resin composition for IC heat resistant tray with improved conductivity - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent electrical conductivity,
The present invention also relates to a heat-resistant tray for ICs having excellent moldability and heat resistance.

[0002]

2. Description of the Related Art If an IC component absorbs moisture, it hardens the epoxy material to be enclosed, and when heated to 100.degree. C. or more, water vapor is generated inside the device during heating, causing blisters or cracks and causing breakage. For this reason, baking is performed in advance at a temperature of 100 ° C. or more. At this time, an IC tray made of a conductive material of 10 ⁸ Ω or less is used to protect the IC. Conventionally, this tray was made of polyamide resin, polyester resin, etc., but in recent years, for the purpose of improving productivity, baking time has been shortened due to temperature rise, and from the viewpoint of economical and environmental problems, conventional disposable trays have been reused. Are being promoted, and a higher temperature type is required.

As a molding material for IC members, Japanese Patent Laid-Open No. 2-17
No. 5754 discloses that the heat distortion temperature is 130 ° C. or higher and the melt flow index is 3 g / 10 min (JIS-K72).
A molding material has been proposed in which the molded article has a surface resistance of 10 ⁷ or less and a polyphenylene ether resin content of at least 50% by weight or more. Specifically, as means for satisfying these physical properties,
Two methods have been proposed in which an acid imide compound is added to a polyphenylene ether resin / conductive carbon system or a polyphenylene ether resin having a low intrinsic viscosity is used.

Japanese Patent Application Laid-Open No. 2-180958 discloses an IC for an IC molded from a resin composition obtained by adding an ABA ′ type hydrogenated block copolymer elastomer to a polyphenylene ether resin / conductive carbon system. Heat resistant trays have been proposed. However, these materials do not sufficiently solve the problems such as exfoliation of molded articles, and the improvement of fluidity is also insufficient.

[0005] Japanese Patent Application Laid-Open No. 2-285302 has a similar proposal. Japanese Patent Publication No. 57-56941 discloses that impact resistance is improved by adding a hydrogenated styrene-butadiene-styrene block copolymer to a polyphenylene ether resin. The composition shown in the article has insufficient compatibility, has a problem of peeling, and has problems such as a decrease in fluidity.

Further, Japanese Patent Application Laid-Open No. 3-37258 describes a method for producing a tray for transporting semiconductor integrated circuit devices comprising a polyphenylene ether polymer / polystyrene polymer / carbon black / ethylene-acrylate copolymer resin. . JP-A-3-143954 discloses that
A heat-resistant conductive tray having a composition obtained by adding high-flowability polypropylene to the above composition has been proposed. In these Examples and Comparative Examples, it is described that 3.7 parts of zinc stearate is added to 100 parts by weight of the polyphenylene ether polymer / polystyrene polymer.

[0007]

Among the problems of the prior art, the addition of conductive carbon improves the conductivity of a resin, but generally results in a decrease in moldability. there were. On the other hand, conductive carbon is expensive, and therefore, in terms of economy, addition of a small amount is preferable.
It was necessary to obtain a heat-resistant tray material for ICs exhibiting greater conductivity with a small amount.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on heat-resistant tray materials for ICs having excellent conductivity, excellent moldability, and excellent heat resistance. That is,
The present invention is; (I) a polyphenylene ether resin 10 wt% or more, (II) an aromatic vinyl compound polymer and an aromatic vinyl reduction
Of Block Copolymer of Compound and Conjugated Diene Compound
Additive, or aromatic vinyl compound and conjugated diene compound
(III) 3 to 40 parts by weight of conductive carbon, and (IV) 0.01 to 3 parts by weight of an organometallic compound per 100 parts by weight of a composition comprising 90% by weight or less of a hydrogenated product of the block copolymer of parts, the resin composition for IC trays more composed and a heat-resistant IC trays material using the same.

That is, the present inventors have developed a polyphenylene ether resin, an aromatic vinyl compound and a conjugated diene compound.
It has been found that by dispersing an organometallic compound in the hydrogenated product of the block copolymer and conductive carbon, it is possible to obtain a heat-resistant tray material for ICs having excellent conductivity, moldability, and heat resistance. This has led to the present invention.
The polyphenylene ether-based resin used in the present invention is represented by the following general formula (1):

[0010]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, hydrogen, etc., and R ₅ and R ₆ are not hydrogen at the same time. And (b) a homopolymer or copolymer can be used. Representative examples of the homopolymer of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether and poly (2 , 6-Diethyl-1,4-phenylene) ether,
Poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-)
1,4-phenylene) ether, poly (2-methyl-6)
-N-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-)
1,4-phenylene) ether, poly (2-methyl-6)
-Hydroxyethyl-1,4-phenylene) ether,
Homopolymers such as poly (2-methyl-6-chloroethyl-1,4-phenylene) ether are exemplified.

The polyphenylene ether copolymer is 2,2
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol or copolymer of o-cresol or 2,3,6-trimethylphenol and o-cresol
Includes polyphenylene ether copolymers having a polyphenylene ether structure as a main component, such as copolymers with cresol.

In the polyphenylene ether resin of the present invention, various other phenylene ether units which have been proposed to be allowed to exist in the polyphenylene ether resin so far as they do not contradict the gist of the present invention are used. It may be included as a partial structure. Japanese Patent Application No. 63-1 / 1988 discloses an example of a proposal for coexistence in a small amount.
2- (dialkylaminomethyl) -6 described in JP-A-2698 and JP-A-63-301222.
-Methylphenylene ether unit and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit.

The polyphenylene ether resin also includes a resin in which a small amount of diphenoquinone or the like is bonded in the main chain.
Further, for example, Japanese Unexamined Patent Application Publication No.
108059 and JP-A-59-59724, which include polyphenylene ethers modified with compounds having a carbon-carbon double bond.

The polyphenylene ether resin used in the present invention has a number average molecular weight of 1,000 to 10
It is 0000. The preferred range is about 6,000
~ 60,000. The number average molecular weight in the present invention is a number average molecular weight in terms of polystyrene obtained by gel permeation chromatography using a standard polystyrene calibration curve.

[0016] Next, in the aromatic vinyl compound-based polymer used in the present invention, styrene, alpha-methyl styrene, homopolymers of vinyl toluene, copolymers thereof, other ethylenically unsaturated monomers And the like. Furthermore, fragrance reinforced these resins with elastomeric
A group vinyl compound polymer may be used. Examples of specific comonomers include α-methylstyrene, acrylonitrile, methacrylonitrile, acrylates, methacrylates, maleic anhydride, N-alkylmaleimides, N-arylmaleimides, vinyloxazoline and the like. is there.

The essential component includes a hydrogenated product of a block copolymer comprising an aromatic vinyl compound and a conjugated diene compound .

Preferred among them are at least one
Aromatic vinyl compound polymer block A and at least one
A block copolymer comprising a plurality of conjugated diene compound polymer blocks B, and the aromatic copolymer in this block copolymer.
The conjugated diene compound polymer block B contains an aromatic vinyl compound and a conjugated diene compound having a degree of unsaturation of 20% or less in the conjugated diene compound polymer block B. It is a hydrogenated product of a block copolymer.

[0019] The conjugated diene compound <br/> compound polymer block of the block copolymer, butadiene, isoprene, 1,
At least one selected from conjugated diolefins such as 3-pentadiene is a polymer block having a polymerized or copolymerized form, and the degree of unsaturation of the block is 20% or less.

The conjugated diene compound polymer block may be randomly copolymerized with an aromatic vinyl compound as long as its properties are not impaired.

A block copolymer composed of an aromatic vinyl compound-based polymer block and a polymer block mainly composed of a conjugated diene compound (hereinafter referred to as "block copolymer as precursor"). Aromatic bi comprising
As the carbonyl compound, styrene, α-methylstyrene,
One or more of vinyl toluene and the like are selected, and styrene is particularly preferable.

The conjugated diene compound is selected from butadiene, isoprene, 1,3-pentadiene and the like.
Species or two or more are selected, and among them, butadiene and / or isoprene are particularly preferred. In the “block copolymer as a precursor”, the weight ratio of the content of the aromatic vinyl compound to the content of the conjugated diene compound is 10/90 to 9/90.
The range of 0/10 is preferable, and the range of 15/85 to 85/15 is more preferable.

The block copolymer has a number average molecular weight of 2,000 to 500,000, preferably 20,000.
It is preferably in the range of 0 to 300,000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably in the range of 1.05 to 10. The molecular structure of the block copolymer may be linear, branched, radial, or a combination thereof. Among them, those having a linear structure are more preferable.

The method for producing the "block copolymer as a precursor" is described in, for example, JP-B-36-19286, JP-B-43-14779, and JP-B-49-36.
957, JP-B-48-2423, JP-B-4
8-4106, and the like. All of these use an organic lithium compound or the like as an anionic polymerization initiator in a hydrocarbon solvent, and if necessary, use a vinylating agent, a coupling agent, etc., to obtain an aromatic vinyl compound and a conjugated diene compound. Is a block copolymerization method.

The above-mentioned "block copolymer as a precursor" is hydrogenated by a known method, for example, the method described in JP-B-42-8704, to obtain a block copolymer preferably used in the present invention. Is obtained. These block copolymers may be used as they are, or may be used after being modified by a conventionally known method such as maleic anhydride.

Further, these block copolymers may be used alone or in combination of two or more. The conductive carbon used in the present invention is dispersed in the composition to impart conductivity,
It is used for the purpose of greatly reducing the surface resistance of the resin molded article, and acetylene black, furnace black, and the like can be used. Specific examples of furnace black include Ketjen Black EC, EC600JD
(Akzo), Asahi HS-500 (Asahi Carbon),
Commercial products such as Vulcan XC72 (manufactured by CABOT) can be used.

The amount of the conductive carbon is 3 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the polyphenylene ether resin and the block copolymer of the present invention. Parts by weight. If the amount is less than 3 parts by weight, the conductivity is insufficient. If the amount exceeds 40 parts by weight, the fluidity and the mechanical strength are reduced, and it is difficult to obtain a good resin molded body.

The metal in the organometallic compound used in the present invention is a group I or II except for hydrogen in the periodic table.
Group, Group III excluding boron, IV excluding carbon and silicon
Group, group VIII, and each subgroup a of group V, VI, and VII. These elements are added, for example, in the form of an organic metal salt, a metal complex, or the like. Examples of the organic component include aliphatic / aromatic carboxylic acids, aliphatic / aromatic sulfonic acids, diketones, alcohols, and phenols. Examples of specific compounds include stearic acid,
12-hydroxystearic acid, montanic acid, behenic acid, lauric acid, myristic acid, butyric acid, acetic acid, maleic acid, cyclohexylbutyric acid, aliphatic carboxylic acid salts such as ethylenediaminetetraacetic acid, benzoic acid, salicylic acid, aliphatic alkyl-substituted benzoic acid , Aromatic carboxylate such as phthalic acid, alkylbenzenesulfonic acid, phenolsulfonic acid, sulfonate such as aliphatic sulfonic acid, diketone complex such as acetylacetone, methanol, ethanol, propanol, butanol, pentanol, hexanol,
Examples include alkoxides such as heptanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, and phenoxides such as phenol, aliphatic alkyl-substituted phenol, and catechol.

The amount of the organic metal compound to be added is 0.01 to 3 parts by weight, preferably 0.05 to 2.8 parts, based on 100 parts by weight of the polyphenylene ether resin and the block copolymer.
Parts by weight. If the addition amount is small, the effect of improving the conductivity is not obtained, and if the addition amount is large, the heat resistance is reduced, and troubles during molding such as silver and adhesion to a mold are caused. The resin composition of the present invention has an antistatic agent as long as its characteristics are not impaired.
Inorganic fillers, various stabilizers, plasticizers, flame retardants, pigments and the like can be appropriately added and used according to a known method.

The method for molding the heat-resistant tray for IC from the resin composition of the present invention is not particularly limited, and a method generally used for molding with an injection molding machine or a method using a melt press is used.

[0031]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In addition, each measurement was performed on condition of the following. Viscosity of polymer: 30% 0.5% chloroform solution
C. using an Ubbelohde viscometer under the condition of
Expressed by c.

Gel permeation chromatography (hereinafter GPC); HL-802 manufactured by Toyo Soda Kogyo Co., Ltd.
Measure by RTS. As a calibration curve in GPC, one prepared using standard polystyrene is used. Melt flow rate: measured at 280 ° C. under a load of 10 kg.

Thermal deformation temperature: Measured under a load of 18.6 kg / cm ² according to ASTM D-648. Izod impact strength; measured according to ASTM D-256. Phase peelability: The vicinity of the gate of an injection-molded 1 / 8-inch thick dumbbell specimen is bent and broken, and the fractured surface is evaluated by visual observation.

Conductivity The surface resistivity is measured according to ASTM D-257. Preparation of unmodified polyphenylene ether resin {n}; raw materials and unmodified poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter abbreviated as PPE) are disclosed in US Pat.
It is produced by oxidative coupling polymerization of 2,6-xylenol in the presence of dibutylamine according to the method described in JP-A-88,277 (Japanese Patent Application No. 62-77570). Raw PPE produces ηsp / c = 0.545, and unmodified PPE produces ηsp / c = 0.462.

Preparation of modified polyphenylene ether resin {a}; 2 parts by weight of maleic anhydride, 100 parts by weight of PPE (ηsp / c = 0.545), perbutyl D0.
After uniformly mixing 5 parts by weight, using an extruder, the mixture was melt-kneaded at 300 ° C. under a nitrogen atmosphere, and a maleation reaction was performed to obtain a modified polyphenylene ether resin. The amount of maleic anhydride added to 100 parts by weight of the polyphenylene ether resin determined by titration with sodium methylate was 0.8 part by weight.

Preparation of the modified polyphenylene ether resin {b}; the viscosity of the raw material PPE obtained in the preparation of the unmodified polyphenylene ether resin {n} is 0.545,
The glass transition temperature is about 208 ° C. As a result of analysis by ¹ H-nuclear magnetic resonance spectrum, the following equation (2) was obtained.

[0037]

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It is confirmed that there are 0.32 terminal groups per 100 main repeating units of the following formula (3).

[0039]

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The amount of free phenolic hydroxyl groups is 0.34 per 100 main repeating units of formula (3).
It is confirmed that there is one. After uniformly blending 10 parts by weight of styrene with 100 parts by weight of this polyphenylene ether using a Henschel mixer, a twin-screw extruder having a screw diameter of 30 mmφ (PCM manufactured by Ikegai Iron Works Co., Ltd.)
−30) The mixture is melt-kneaded at 300 ° C. and pelletized through a water tank.

The pellet obtained in this manner was treated with ¹ H-
As a result of analysis by a nuclear magnetic resonance spectrum, the following equation (4) was obtained.

[0042]

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The terminal group of the above is a main repeating unit represented by the formula (3)
It is 5.0 per 100
It is confirmed from the area value of the signal of 2 ppm. In addition, it is confirmed that the amount of free phenolic hydroxyl groups is 0.45 per 100 main repeating units of the formula (3). The number average molecular weight determined by GPC is 24,50.
0 and the viscosity is 0.547.

[0044]

Example 1 Modified polyphenylene ether resin {b} 8
6 parts by weight of Ketjen Black EC600JD (conductive carbon) with respect to 100 parts by weight of a composition composed of 0% by weight, 17% by weight of a block copolymer (A), and 3% by weight of a block copolymer (B). , The organometallic compound of Table 1 was added to 0.
One part by weight is mixed, melt-kneaded at 320 ° C. in a twin-screw extruder, and pelletized. The pellets are converted into 33
Molding and test pieces are prepared at 0 ° C. and evaluated.

As the block copolymer (A) (hydrogenated styrene-butadiene block copolymer), those having the following properties are used. Styrene content: 60% by weight Number average molecular weight: 8.0 × 10 ⁴ Unsaturation: 2% The block copolymer (B) (hydrogenated styrene-butadiene block copolymer) has the following properties: Is used.

Styrene content: 40% by weight Number average molecular weight: 5.0 × 10 ⁴ Unsaturation: 2%

[0047]

Example 2 Modified polyphenylene ether resin {b} 8
6 parts by weight of Ketjen Black EC600JD (conductive carbon) with respect to 100 parts by weight of a composition composed of 0% by weight, 17% by weight of a block copolymer (A), and 3% by weight of a block copolymer (B). , The organometallic compound of Table 1 was added to 0.
5 parts by weight are mixed, melt-kneaded at 320 ° C. in a twin-screw extruder, and pelletized. The pellets are converted into 33
Molding and test pieces are prepared at 0 ° C. and evaluated.

The properties of the block copolymer (A) and the block copolymer (B) are the same as in Example 1.

[0049]

Examples 3 and 4 80 parts by weight of modified polyphenylene ether resin {b}, 17 parts by weight of block copolymer (A), 3 parts by weight of block copolymer (B), based on 100 parts by weight of a composition comprising , Ketchen Black EC600
6 parts by weight of JD (conductive carbon) and 0.5 parts by weight of the organometallic compound shown in Table 1 were mixed and mixed at 320 ° C. in a twin screw extruder.
And melt-kneaded into pellets. The pellets are molded by an injection molding machine at 330 ° C., test pieces are prepared, and evaluated.

The properties of the block copolymer (A) and the block copolymer (B) are the same as in Example 1.

[0051]

Comparative Examples 1-4 Based on 100 parts by weight of a composition comprising a modified polyphenylene ether resin {b} 80% by weight, a block copolymer (A) 17% by weight, and a block copolymer (B) 3% by weight. The amounts of the conductive carbon and the organometallic compound shown in the table (Comparative Examples 1 and 2 were not added) were mixed, melt-kneaded at 320 ° C. in a twin-screw extruder, and pelletized. The pellets are molded by an injection molding machine at 330 ° C., test pieces are prepared, and evaluated.

The properties of the block copolymer (A) and the block copolymer (B) are the same as in Example 1.

[0053]

Examples 6 to 13 Composition 1 comprising the modified polyphenylene ether resin {n} or {a} or {b} shown in the table, block copolymer (A), block copolymer (B)
With respect to 00 parts by weight, the amounts of the conductive carbon and the organometallic compound shown in the table are mixed, melt-kneaded at 320 ° C. in a twin-screw extruder, and pelletized. The pellets are molded by an injection molding machine at 330 ° C., test pieces are prepared, and evaluated.

The properties of the block copolymer (A) and the block copolymer (B) are the same as in Example 1.

[0055]

Comparative Examples 5 to 7 Composition 10 comprising the modified polyphenylene ether resin {n} or {a} or {b} shown in the table, block copolymer (A), block copolymer (B)
The conductive carbon shown in the table is mixed with 0 parts by weight, melt-kneaded at 320 ° C. in a twin-screw extruder, and pelletized. The pellets are molded by an injection molding machine at 330 ° C., test pieces are prepared, and evaluated.

The properties of the block copolymer (A) and the block copolymer (B) are the same as in Example 1.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

As is clear from Tables 1, 2 and 3, the compositions of Examples 1 to 13 are excellent in both conductivity, releasability and fluidity, and have excellent properties as a resin composition for IC trays. doing.

[0061]

The molding material of the present invention exhibits good conductivity and heat resistance, reduces the amount of conductive carbon to be added, has no problems such as phase separation, and is suitable as an IC tray material.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI H01L 23/29 H01L 23/30 R 23/31

Claims (3)

(57) [Claims] (I) Polyphenylene ether resin 1
0% by weight or more , (II) an aromatic vinyl compound-based polymer ,
Block copolymer of aromatic vinyl compound and conjugated diene compound
Conjugated with hydrogenated polymer or aromatic vinyl compound
(III) 3 to 40 parts by weight of conductive carbon, and (IV) 0.01% by weight of an organometallic compound per 100 parts by weight of a composition comprising 90% by weight or less of a hydrogenated product of a block copolymer with a diene compound. 1 to 3 parts by weight of a resin composition for an IC tray . (I) Polyphenylene ether resin
Has been modified by a compound having a carbon-carbon double bond.
A modified polyphenylene ether;
The resin composition according to claim 1. 3. A process according to claim 1 or 2 of the IC heat-resistant tray molded from the resin composition according to any one.