TW201345968A - Resin composition - Google Patents

Abstract

The present invention relates to a resin composition including a cyclic olefin homopolymer (A) having a glass transition temperature of 101 DEG C to 160 DEG C, a fibrous electrically-conductive filler (B), and at least one elastomer (C) selected from the group of consisting an olefin-based elastomer, and a styrene-based elastomer, wherein the amount of the elastomer (C) is 5 to 25 parts by mass, relative to 100 parts by mass of the cyclic olefin homopolymer (A). The present invention can provide a resin composition which can be used to obtain a resin molded product having high mechanical strength, heat resistance, high conductivity, and a small amount of outgassing.

Description

Resin composition Field of invention

The present invention relates to a resin composition.

The present invention claims priority based on Japanese Patent Application No. 2012-085075, the entire disclosure of which is incorporated herein by reference.

Background of the invention

In the semiconductor manufacturing process, a semiconductor storage transport container made of a resin molded body is used to transport or store a wafer or the like.

In terms of the performance required for the semiconductor storage and transportation container, it is excellent in mechanical strength and heat resistance for bending and punching, and further excellent in antistatic property (that is, electrical conductivity) to prevent adhesion of dirt and dust or a circuit. Damage, etc.

As a resin composition for providing such a semiconductor storage and transport container, for example, a cyclic olefin copolymer, an olefin resin, and a conductive filler are proposed (see Patent Document 1).

Further, a cyclic olefin polymer having a specific glass transition temperature of a melt kneading material is proposed, and a glass obtained by polymerizing two or more kinds of monomers selected from the group consisting of an olefin, a diene, and an aromatic vinyl hydrocarbon is proposed. Transfer temperature is below 0 °C A soft copolymer, a radical initiator, and a resin composition having a polyfunctional compound having two or more radical polymerizable functional groups in a molecule (see Patent Document 2).

[Advanced technical literature] [Patent Literature]

Patent Document 1 Japanese Patent Laid-Open No. 7-118465

Patent Document 2 International Publication No. 2006/025294.

Summary of invention

In recent years, in addition to the miniaturization of the semiconductor circuit pattern, the semiconductor storage and transport container is particularly strict in terms of mechanical strength, heat resistance, and electrical conductivity, and does not become a source of pollution itself. Specifically, since the outgas generated from the resin composition of the material of the semiconductor storage and transport container contaminates the wafer or the like, it is easy to cause a defect in the formation of the circuit pattern, and therefore, it is more desirable to reduce the amount of outgassing (low outgassing) Sex). By reducing the amount of outgassing, wafer productivity can be increased. However, the techniques described in Patent Documents 1 and 2 do not sufficiently suppress the generation of outgas.

The present invention has been made in view of the above circumstances, and it is a resin composition which is excellent in mechanical strength, heat resistance, electrical conductivity, and low outgassing when a molded article is produced.

As a result of intensive investigation, the present inventors have provided the following means to solve the above problems.

That is, one aspect of the resin composition of the present invention is characterized by The invention comprises a cyclic olefin homopolymer (A) having a glass transition temperature of 101 to 160 ° C, a fibrous conductive filler (B), and a group selected from the group consisting of an olefin elastomer and a styrene elastomer. At least one of the elastomers (C); and the content of the elastomer (C) is 5 to 25 parts by mass based on 100 parts by mass of the cyclic olefinic polymer (A).

The resin composition of the present invention preferably further comprises polyethylene (D) having a viscosity average molecular weight of 1,000,000 or more.

Further, the resin composition of the present invention preferably further contains a particulate conductive filler (E). The particulate conductive filler (E) has a carbon black having a di-n-butyl phthalate oil absorption of 180 mL/100 g or more.

According to the present invention, a resin composition excellent in any of mechanical strength, heat resistance, electrical conductivity, and low outgassing property can be provided when a molded article is produced.

Form for implementing the invention

<Resin composition>

The resin composition of the present invention comprises: a cyclic olefin homopolymer (A) having a glass transition temperature of 101 to 160 ° C, a fibrous conductive filler (B), and an olefin-based elastomer and a styrene-based compound. At least one elastomer (C) of the group of elastomers. Hereinafter, these components are also referred to as component (A), component (B), and component (C), respectively.

The resin composition of the present invention can be suitably used as a member of an electronic component, or a material of a container or a jig used in a manufacturing process of an electronic component. In particular, it is suitable as a material for a transport container (FOUP: Front Opening Unified Pod) used for transporting a wafer or the like, and a photomask case for storing a photomask which is necessary for pattern formation.

(Rected olefin homopolymer (A) with a glass transition temperature of 101-160 ° C)

In the present invention, the component (A) is used as a base resin of a resin composition. The resin composition contains the component (A) and is excellent in low outgassing properties in addition to heat resistance. In addition, since the component (A) has a low water absorption property compared with other types of thermoplastic resins, moisture is prevented from adhering to the wafer or the like when the resin composition containing the component (A) is formed into a molded body.

The "cyclic olefin homopolymer" is a polymer (homopolymer) in which a cyclic olefin is a monomer and a cyclic olefin is homopolymerized, and the main chain of the polymer has carbon-carbon. A polymer compound of a cyclic hydrocarbon structure composed of a bond.

The cyclic olefin is a cyclic hydrocarbon having at least one olefin (double bond) typified by norbornene and tetracyclododecene.

The cyclic olefin is preferably a polycyclic olefin represented by norbornene or tetracyclododecene.

The (A) component is a ring-opening polymer having a monomer having a norbornene ring, or a hydrogenated product thereof, which is disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei.

Examples of the monomer having a norbornene ring include a cyclodecene which is a bicycloolefin of an adduct of ethylene and cyclopentadiene, and a tetracyclic ring of a cycloolefin which is a cyclopentadiene-added norbornene. Tricyclodecadiene (also known as dicyclopentadiene), a dodecene, a cyclopentadiene dimer tricyclodiene a tricyclodecene which saturates a saturated tricyclic olefin by hydrogenating a part of the unsaturated bond of dicyclopentadiene, and a pentacyclic fifteen carbon of a pentacyclic diene which is a cyclopentadiene trimer Pentacyclo pentadecadiene, a pentacyclopentene (also known as 2,3-dihydrogen) of a saturated pentacyclic olefin by hydrogenating a portion of the unsaturated bond of pentacyclopentadiene Dicyclopentadiene) or such substituted or the like.

Examples of such a substituent include a derivative substituted with a group having no polar group (alkyl group, alkylene group, aromatic group, etc.) or a hydrogenated product thereof, or a dehydrogenation product derived therefrom. Derivatives (for example, 2-northene, 5-methyl-2-northene, 5,5-dimethyl-2-northene, 5-ethyl-2-northene, 5-butyl Base-2-northene, 5-ethylidene-2-norbornene, 5-hexyl-2-northene, 5-phenyl-2-northene, 5-octyl-2-norbornene a norbornene derivative such as aene, 5-octadecyl-2-northene, 5-ethylidene-2-northene; 1,4:5,8-dimethyl bridge-1,2,3, 4,4a,5,8,8a-2,3-cyclopentadieno octahydronaphthalene, 6-methyl-1,4:5,8-dimethyl bridge-1,4,4a,5 ,6,7,8,8a-octahydronaphthalene, 1,4:5,10:6,9-triple bridge-1,2,3,4,4a,5,5a,6,9,9a,10, a tetracyclododecene derivative such as cyclopentadieno anthracene, etc.; a polar group (a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, etc.) a derivative substituted with amidino, quinone, fluorenyl or the like (for example, 5-methoxy-carbonyl-2-northene, 5-cyano-2-northene, 5-methyl- 5-methoxycarbonyl- 2-northene, etc.).

In the present invention, "glass transition temperature (Tg)" is a value measured by a method in accordance with JIS K 7121.

The Tg of the component (A) is 101 to 160 ° C, preferably 101 to 150 ° C, and more preferably 101~140°C, especially good 102~140°C, best system 105~140°C. When the Tg of the component (A) is 101 ° C or more, the amount of outgassing is easily reduced. In addition, heat resistance is further improved. When the Tg is 160 ° C or less, it is easy to reduce the amount of outgassing.

In the resin composition, the component (A) may be used singly or in combination of two or more.

Among them, since the effect of the present invention is more excellent, the component (A) is preferably a ring-opening polymer having a Tg of 101 to 160 ° C and having a monomer of a norbornene ring or a hydrogenated product thereof, particularly preferably the above-mentioned ring-opening polymer. Hydride.

Further, the number average molecular weight of the component (A) is preferably from 3,000 to 500,000, more preferably from 8,000 to 200,000. Here, the number average molecular weight means a value calculated by gel permeation chromatography (hereinafter referred to as GPC) using cyclohexane as a solvent and converted by isoprene.

A commercially available product can be used as the component (A). ZEONEX (registered trademark) and ZEONOR (registered trademark) which are suitable for the above-mentioned commercial products (all of which are trade names, manufactured by Nippon Zeon Co., Ltd.).

When the total amount of the resin composition is 100% by mass, the content of the component (A) in the resin composition is preferably 60 to 90% by mass, more preferably 70 to 90% by mass.

If the content of the component (A) is less than the preferred lower limit, the low outgassing property as a resin composition is liable to be impaired. If it exceeds the preferable upper limit, the component other than the component (A) cannot be sufficiently blended, and when the molded article is produced, it is difficult to obtain the adhesion reducing effect and the mechanical strength (impact strength) of dirt, dust, and the like. In other words, when the content of the component (A) is 60 to 90% by mass based on 100% by mass of the resin composition, a resin composition having excellent low outgassing property can be obtained. Further, it is preferable that the other components can be sufficiently blended to impart adhesion reduction effect and mechanical strength to dirt, dust, and the like.

(fibrous conductive filler (B))

In the present invention, the component (B) mainly contributes to imparting conductivity and improving mechanical strength (bending strength) and heat resistance.

The "fibrous conductive filler" is a fibrous particle defined in JIS K 3850 "Method for Measuring Fibrous Particles in Air", that is, the aspect ratio (length (fiber length) / width (fiber diameter)) is More than 3 conductive fillers. Here, the "fiber diameter" means the diameter (thickness) of the fibrous conductive filler. Further, the term "fiber length" means the length of the fibrous conductive filler. These can be determined by observation using a microscope.

In one aspect of the present invention, the aspect ratio of the component (B) is preferably from 3 to 3,000, and more preferably from 50 to 2000 from the viewpoint of handling and strength reinforcement.

Carbon fiber, a carbon nanotube or the like can be used as the component (B).

When the carbon fiber is used, the type of the carbon fiber is not particularly limited, and various materials such as polyacrylonitrile (PAN), pitch, cellulose, and lignin may be mentioned. Among them, from the viewpoint of strength reinforcement, PAN-based or pitch-based carbon fibers are preferably used. Further, from the viewpoint of improving the handleability, it is preferred to use a fiber length of 3 to 6 mm which is bundled by the sizing agent. Here, the sizing agent refers to a sizing agent added to carbon fibers for the purpose of enhancing the dispersion of carbon fibers into a resin and improving handleability. From the viewpoint of dispersibility of the resin, it is preferred to use an epoxy resin, an ethyl urethane or a sizing agent having an epoxy resin and an ethyl urethane in combination as a sizing agent. Also, when When the carbon fiber bundled with the sizing agent is used as the component (B), the component (B) preferably contains the sizing agent and the carbon fiber.

The fiber diameter should be in the range of 5 to 15 μm, preferably in the range of 5 to 12 μm, and more preferably in the range of 6 to 10 μm. In addition, the impregnation rate of the sizing agent is preferably 3% by mass or less, and preferably 1 to 3% by mass based on the entire carbon fiber (100% by mass). As a commercial item, NPS chopped fiber (manufactured by NIHON POLYMER Co., Ltd.), PAN-based carbon fiber, sizing agent: epoxy urethane (epoxyurethane) ) 1.75%, fiber length: 6 mm), TORAYCA (registered trademark) (Toray Industries, Inc., PAN-based carbon fiber, sizing agent: ethyl urethane 3.0%, fiber length: 6 mm) , PYROFIL (registered trademark) (manufactured by Mitsubishi Rayon Co., Ltd., PAN carbon fiber, sizing agent: 3.0%, fiber length: 6 mm).

When a carbon nanotube is used, any one of a multi-walled carbon nanotube having a structure in which one layer of graphite is rolled and a multi-walled carbon nanotube having a structure in which two or more layers of graphite are wound may be used. Among them, multi-walled carbon nanotubes should be used. The fiber diameter and the fiber length have the effects of the present invention, and the aspect ratio is preferably 3.0 or more and 250 or less, and is not particularly limited. Commercially available products include VGCF (registered trademark) and VGCF-X (registered trademark) (all of which are manufactured by Showa Denko Co., Ltd.).

In the resin composition, the component (B) may be used singly or in combination of two or more.

The content of the component (B) in the resin composition is not particularly limited as long as it has the effects of the present invention, and is preferably 3 to 25 in terms of 100 parts by mass of the component (A). The amount is preferably 3 to 20 parts by mass, 3 to 15 parts by mass, and 4 to 15 parts by mass. When the content of the component (B) is less than 3 parts by mass based on 100 parts by mass of the component (A), it becomes difficult to obtain sufficient conductivity. Further, if it exceeds 25 parts by mass, it is easy to cause a decrease in the impact resistance.

In addition, when the resin composition is 100% by mass as a whole, the content of the component (B) in the resin composition is preferably 2 to 25% by mass, preferably 3 to 20% by mass, and particularly preferably 3 to 12% by mass. %. In the resin composition, if the content of the component (B) is less than 2% by mass, it becomes difficult to obtain sufficient conductivity. Further, if the content of the component (B) exceeds 25% by mass, it is likely to cause a decrease in the impact resistance. In other words, when the content of the component (B) is from 3 to 25 parts by mass based on 100 parts by mass of the component (A), or when the total amount of the resin composition is 100% by mass, it may be 2 to 25% by mass. It is preferable that sufficient conductivity is obtained and the impact resistance of the molded body is not lowered.

(selected from at least one elastomer (C) in the group consisting of an olefin-based elastomer and a styrene-based elastomer)

In the present invention, the component (C) mainly contributes to an improvement in mechanical strength (impact strength).

The term "elastomer" means a polymer material which is an elastomer at normal temperature (25 ° C). The polymer material may be a natural polymer material or a synthetic polymer material.

The olefin-based elastomer (hereinafter also referred to as "(C1) component") is a mixture of carbon atoms and hydrogen atoms obtained by polymerizing the olefin as an olefin and does not have an aromatic ring at room temperature (25 ° C). The polymer material is an elastomer. That is, in one aspect of the present invention, as an olefin-based elastic The monomer of the body is preferably an ethylene, propylene or butylene-based olefin and polymerized with ethylene, propylene or butene as a co-monomer. Among them, an olefin-based elastomer having a low glass transition temperature is preferred.

Further, the glass transition temperature of the component (C1) is preferably -100 to -10 ° C, preferably -65 ° C to -50 ° C.

Industrially, ESPOLEX TPE (trademark registration) (manufactured by Sumitomo Chemical Co., Ltd.), Sarlink (trademark registration) (TOYOBO CO., LTD) can be suitably used. System, THERMORUN (trademark registration) (manufactured by Mitsubishi Chemical Corporation), TAFMER (trademark registration) (Mitsui Chemicals, Inc.), MILASTOMER (trademark registration) (manufactured by Mitsui Chemicals, Inc.) (Available as a product name) (all of the above). Among them, TAFMER and MILASTOMER (manufactured by Mitsui Chemicals, Inc.) are preferred.

The styrene-based elastomer (hereinafter also referred to as "(C2) component") is a monomer based on styrene and using butadiene and butene as a monomer, and the monomer is obtained by polymerizing the monomer. The polymer material which is an elastomer at room temperature (25 ° C) is represented by an aromatic vinyl-conjugated diene block copolymer. That is, in one aspect of the invention, the styrene-based elastomer is preferably styrene/butadiene/styrene (SBS), styrene/butadiene/butene/styrene (SBBS), styrene. /ethylene/butene/styrene (SEBS), wherein SEBS is preferred from the viewpoint of compatibility.

Industrially, it is suitable to use Tufprene (trademark registration) (Asahi Kasei Chemicals Corporation), Tuftec (trademark registration) (made by Asahi Kasei Co., Ltd.), Kraton (trademark registration) (Kraton Performance Polymers Inc.), ESPOLEX SB (trademark registration) (manufactured by Sumitomo Chemical Co., Ltd.) Commercial products such as RABALON (trademark registration) (manufactured by Mitsubishi Chemical Corporation) and SEPTON (trademark registration) (manufactured by Kuraray Co., Ltd.) (all of which are trade names). Among them, SEPTON (manufactured by Kuraray Co., Ltd.) and Tuftec (manufactured by Asahi Kasei Co., Ltd.) are preferable.

In the resin composition, the (C1) component or the (C2) component may be used alone or in combination of two or more. The component (C1) and the component (C2) may be used in combination.

The content of the component (C) in the resin composition is 5 to 25 parts by mass, preferably 5 to 20 parts by mass, preferably 7 to 20 parts by mass, based on 100 parts by mass of the component (A), and particularly preferably 7 to 20 parts by mass. 15 parts by mass, the best system is 9 to 15 parts by mass.

If the content of the component (C) is less than 5 parts by mass, the effect of improving the punching resistance is insufficient, and if it exceeds 25 parts by mass, the heat resistance is lowered and the mechanical strength is lowered. Also, the amount of outgassing is also increased.

In addition, when the resin composition is 100% by mass as a whole, the content of the component (C) in the resin composition is preferably 2 to 22% by mass, preferably 3 to 20% by mass. When the content of the component (C) in the resin composition is less than 2% by mass, the effect of improving the punching resistance is insufficient, and if it exceeds 22% by mass, the heat resistance is lowered and the mechanical strength is lowered. Also, the amount of outgassing is also increased. In other words, when the content of the component (C) in the resin composition is 5 to 25 parts by mass, or 2 to 22, when the resin composition as a whole is 100% by mass, the amount of the component (A) is 100 parts by mass. Resin composition resistance The heat and mechanical strength are not lowered, and the amount of outgas production is further reduced, so that it is preferable.

(Polyethylene (D) with a viscosity average molecular weight of 1 million or more)

In addition to the components (A) to (C), the resin composition of the present invention preferably further contains polyethylene (D) having a viscosity average molecular weight of 1,000,000 or more (hereinafter also referred to as "(D) component"). By including the component (D), the abrasion resistance to the wafer or the like is improved and the generation of particles (foreign matter) can be prevented. Further, the weld adhesiveness is also improved, and the resin composition of the present invention can be suitably used for a large-sized semiconductor container.

In the present invention, the "viscosity average molecular weight" means the ultimate viscosity [η] in a decalin solvent at 135 ° C and is based on the formula: [η] = kMν ^α (Mν-based viscosity average molecular weight, k and α-system constant) The calculated value. The ultimate viscosity is determined by the method according to JIS K7367-3 (1999).

The viscosity average molecular weight of the component (D) is 1,000,000 or more, preferably 1,000,000 or more and 6,000,000 or less, preferably 1,000,000 or more and 4,000,000 or less, and particularly preferably 1.2 million or more and 4,000,000 or less, and the optimum system is 1.5 million. Above and below 4 million.

When the viscosity average molecular weight of the component (D) is 1,000,000 or more, the wear resistance and the weldability of the wafer or the like are improved. In particular, the increase in the weldability is considered to be because the viscosity average molecular weight of the component (D) is 1,000,000 or more, and the viscosity of the resin composition is increased, and the adhesion between the resin compositions on the welded surface is improved. On the other hand, if it is preferably at most the upper limit value, the resin composition tends to maintain good impact strength and fluidity. Also, the amount of outgassing is also small. Here, the term "welding property" means a state in which a line (melt line) generated in a portion where a resin composition in a molten state merges in a mold is produced, and the obtained molded body is confirmed by visual observation. Line for evaluation.

In the resin composition, the component (D) may be used singly or in combination of two or more.

Further, since it is easier to uniformly mix, the (D) component is preferably a powder type having a particle diameter of about 10 to 50 μm. Here, the "particle size" refers to a value measured by using a Coulter Particle Size Analyzer TA-II type, a Japanese machine (Company), under the condition that the component (D) is dispersed in water.

A commercially available product can be used as the component (D). As the commercially available product, Hi-zex-million (registered trademark) or MIPELON (registered trademark) containing polyethylene having a viscosity average molecular weight of 1,000,000 or more and 4 million or less as a main component can be suitably used (any one is Mitsui) Chemical Co., Ltd.) and so on. Among these, MIPELON (manufactured by Mitsui Chemicals, Inc.) is preferred.

The content of the component (D) in the resin composition is preferably from 1 to 20 parts by mass, preferably from 5 to 15 parts by mass, per 100 parts by mass of the component (A). With respect to 100 parts by mass of the component (A), if the content of the component (D) is less than the lower limit, the effect of improving the abrasion resistance and the weldability is insufficient, and if it exceeds the preferred upper limit, It is easy to cause a decrease in fluidity when the molded body is formed.

In addition, the content of the component (D) in the resin composition is preferably from 1 to 20 parts by mass, preferably from 5 to 15 parts by mass, per 100 parts by mass of the total of the components (A) to (C). With respect to 100 parts by mass of the total of the components (A) to (C), if the content of the component (D) is less than the lower limit, the effect of improving the abrasion resistance and the weldability is insufficient, and if it is more than When the upper limit is obtained, the fluidity is liable to be lowered when the formed body is formed.

In addition, when the resin composition is 100% by mass as a whole, the resin The content of the component (D) in the composition is preferably from 0.4 to 18% by mass, preferably from 0.5 to 16% by mass. When the content of the component (D) in the resin composition is less than 0.4% by mass, the effect of improving the abrasion resistance and the weldability is insufficient, and if it exceeds 18% by mass, the fluidity is liable to occur when the formed body is formed. The reduction. In other words, the content of the component (D) in the resin composition is from 1 to 20 parts by mass, or 100 parts by mass based on the total of the components (A) to (C), based on 100 parts by mass of the component (A). In the case where the content of the component (D) in the resin composition is from 0.4 to 18% by mass, the abrasion resistance can be sufficiently obtained, and the amount of the resin composition is from 100 to 18% by mass. It is preferable that the effect of improving the weldability is improved and the fluidity is hard to be lowered when the molded body is formed.

(Particulate conductive filler (E))

The resin composition of the present invention may further contain a particulate conductive filler (E) in addition to the components (A) to (C) or the components (A) to (D) (hereinafter also referred to as " (E) Ingredients").

When the formed body is formed by including the component (E), the molded body exhibits a substantially constant surface resistivity (that is, a small difference in conductivity) at any place, and the conductivity can be further stabilized. The reason why such an effect can be obtained is that the component (B) forms a non-uniform conductive network due to a low addition amount, whereas the component (E) functions to form a uniform conductive network even if the amount of the component (E) is low. Therefore. Here, the "surface resistivity" means a value measured by the conditions of ASTM D257 using MCP-HT260 Hiresta IP manufactured by Mitsubishi Chemical Analytech Co., Ltd.

Further, by including the component (E), the warpage at the time of forming the formed body can be reduced The amount of curvature (suppresses the occurrence of warpage due to forming). The reason why such an effect can be obtained is that the aspect ratio of the component (B) in the molded article is high, and the shrinkage ratio between the longitudinal direction and the lateral direction is different at the time of molding, and the orientation of the component (E) in the molded body is different. It is low and the shrinkage ratio of the longitudinal direction and the lateral direction at the time of forming becomes the same.

The component (E) is a conductive filler having an aspect ratio (length (long axis of the particle) / width (short axis of the particle)) of less than 3. In one aspect of the invention, the aspect ratio of the component (E) is preferably 1 or more and less than 3, preferably 1 to 2.

Carbon black, black lead or the like can be used as the component (E). Among them, carbon black is preferred because a conductive network can be formed in the resin composition with a small amount of addition without impairing the impact strength.

The type of carbon black is not particularly limited as long as it has the effects of the present invention, and may be appropriately selected depending on the purpose, and examples thereof include furnace black carbon produced by an oil furnace method, acetylene black produced by using acetylene gas as a raw material, and a closed space. A lamp black produced by directly burning a raw material, a thermal carbon black produced by thermal decomposition of natural gas, and a grooved carbon black obtained by contacting a diffusion flame with a bottom surface of a channel steel.

Among these, from the viewpoints of conductivity, dispersibility in a resin composition, and the like, carbon black having an oil absorption of n-dibutyl phthalate (DBP) of 180 mL/100 g or more is preferable. Preferably, the carbon black having a di-n-butyl phthalate oil absorption of 300 mL/100 g or more is used.

If the DBP oil absorption is less than 180 mL/100 g, the amount of use becomes large in order to obtain the desired effect, and it becomes easy to cause a decrease in the impact resistance. When the DBP oil absorption is 180 mL/100 g or more, the amount can be easily obtained in a small amount. The effect of desire.

In the present invention, "di-n-butyl phthalate (DBP) oil absorption" means a value measured by a method in accordance with ASTM D2414 (using a DBP oil absorption meter).

Further, the carbon black is preferably a furnace black produced by an oil furnace method or an acetylene black produced by using an acetylene gas as a raw material from the viewpoint of conductivity, and the primary particle diameter of the carbon black is preferably 30. ~50nm, preferably 30~40nm. When the primary particle diameter of the carbon black is 30 to 50 nm, the specific surface area is sufficiently large, and the DBP oil absorption amount is preferably in the above preferred range. The above primary particle diameter means a value measured from an electron microscope image.

In the resin composition, the component (E) may be used singly or in combination of two or more.

A commercially available product can be used as the component (E). As the commercially available product, Ketchen black EC 300J (manufactured by Lion King Co., Ltd., primary particle size: 40 nm), Ketchen black EC 600JD (manufactured by Lion King Co., Ltd., primary particle size: 34 nm), VULCAN XC-72 can be suitably used. (manufactured by Cabot Co., Ltd., primary particle diameter: 37 nm), Denka black (manufactured by Electric Chemical Industry Co., Ltd., primary particle diameter: 43 nm) (all of which are trade names), and the like. Among them, Ketchen black EC 300J (manufactured by Lion King Co., Ltd.) and Ketchen black EC 600JD (manufactured by Lion King Co., Ltd.) which can form a conductive network in the resin composition are preferably added in a small amount.

The content of the component (E) in the resin composition is preferably from 1 to 15 parts by mass, preferably from 1 to 12 parts by mass, particularly preferably from 5 to 12 parts by mass, per 100 parts by mass of the component (A). 100 parts by mass of the component (A), if it is contained in the component (E) When the amount is less than the lower limit, it is difficult to sufficiently obtain the effect of setting the surface resistivity when forming the molded body, and suppressing the warpage of the molded body due to the molding, and if it exceeds the preferable upper limit, It is easy to cause a decrease in the resistance to punching. Also, there is a source of pollution.

In addition, the content of the component (E) in the resin composition is preferably from 1 to 12 parts by mass, preferably from 1 to 10 parts by mass, based on 100 parts by mass of the total of the components (A) to (C). 10 parts by mass. With respect to 100 parts by mass of the total of the components (A) to (C), if the content of the component (E) is less than the preferred lower limit, it is difficult to sufficiently obtain the stability effect of the surface resistivity at the time of producing the molded article, and The effect of warpage of the formed body due to molding is suppressed, and if it exceeds the preferable upper limit, the impact resistance is likely to be lowered. Also, there is a source of pollution.

In addition, when the resin composition is 100% by mass as a whole, the content of the component (E) in the resin composition is preferably 0.4 to 15% by mass, preferably 0.5 to 13% by mass, preferably 1 to 12% by mass. Preferably, it is 1 to 10% by mass. In the resin composition, if the content of the component (E) is less than the preferred lower limit, it is difficult to sufficiently obtain the stability effect of the conductivity at the time of forming the molded body, and the effect of suppressing the warpage of the molded body due to the molding. However, if it exceeds the preferred upper limit, it is easy to cause a decrease in the impact resistance. Also, there is a source of pollution. In other words, the content of the component (E) in the resin composition is from 1 to 15 parts by mass, or 100 parts by mass based on the total of the components (A) to (C), based on 100 parts by mass of the component (A). When the amount of the resin composition is from 10 to 15% by mass, the surface resistivity of the molded article can be sufficiently stabilized and suppressed when the amount of the resin composition is from 100 to 15% by mass. The effect of warping of the formed body due to the forming, the punching resistance is not lowered, and the component (E) itself is not It is good to be a source of pollution.

When the component (E) is used, when the total amount of the resin composition is 100% by mass, the total content of the component (B) and the component (E) in the resin composition is preferably 5 to 25% by mass, preferably 5 ~18% by mass.

If the total content of the component (B) and the component (E) is less than the preferred lower limit, it is difficult to obtain the desired conductivity, and if it exceeds the preferred upper limit, the impact resistance is likely to be lowered. In other words, when the total content of the component (B) and the component (E) is 5 to 25% by mass, the desired conductivity can be obtained, and the impact resistance of the molded article can be obtained when the total amount of the resin composition is 100% by mass. It is difficult to reduce, so it is good.

In addition, when the content ratio of the component (B) to the component (E) (the content of the component (B) / the content of the component (E) is 3.0 or less, the effect of suppressing warpage is high, and it is preferable.

The resin composition of the present invention may further contain, as an optional component, a lubricant, a dye, a pigment, various stabilizers, a reinforcing agent, a filler, and the like.

<Method for Producing Resin Composition>

The resin composition of the present invention can be produced by melt-kneading the above components by using a known resin kneading apparatus (for example, a hot rolling mill, a kneading machine, a Banbury mixer, or the like) or a twin-screw kneading extruder. . A pelletizer can also be used to form a pelletized resin composition as needed.

The temperature at which the components are melt-kneaded may be appropriately set depending on the type of the cyclic olefinic polymer (A) to be used, and is usually 200 to 400 °C.

<Manufacturing method of semiconductor storage and transport container (FOUP)>

Then, the resin composition of the present invention (preferably, a resin composition in a pellet form) is used, and injection molding, injection compression molding, and addition are carried out. The formed body can be obtained by press forming, extrusion molding, or blow molding. Here, it is preferable to use injection molding from the viewpoint of the shape and dimensional accuracy of the molded body.

In one aspect of the invention, the method for producing a semiconductor storage container preferably comprises the steps of: melting a resin composition of the present invention (preferably a pelletized resin composition) to obtain a molten resin, and filling the molten resin. A method of obtaining a step of forming a body in a mold. In the step of obtaining the aforementioned molten resin, the temperature for melting the resin composition of the present invention is preferably 260 to 300 °C. Further, in the step of obtaining the formed body, the mold temperature is preferably 50 to 100 ° C, and the forming temperature is preferably 260 to 290 ° C.

By using the resin composition containing the components (A) to (C) of the present invention as a material for the semiconductor storage and transport container, mechanical strength (bending strength, impact strength), heat resistance, electrical conductivity, and low outgassing can be obtained. A molded article (semiconductor storage and transport container) excellent in any of the properties.

For example, according to the transport container (FOUP) formed of the molded body, the mechanical strength is high, and the wafer or the like can be protected from contact with other members. Further, the heat resistance is high, and deformation due to heat can be prevented when the molded body is dried. Further, since it has excellent conductivity, it is difficult to generate static electricity, and further, since the amount of outgas generated is small, it is difficult to become a source of contamination itself, and it is possible to prevent contamination substances from adhering to a wafer or the like. Therefore, the productivity of the wafer can be improved.

Such a resin composition of the present invention is particularly suitably used as an electronic component packaging container used in a manufacturing process of an electronic component, which is strongly required to have a low outgassing accompanying progress in miniaturization of a semiconductor circuit pattern. In particular, it is suitable for use as a semiconductor storage and transport container.

Example

Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited thereto.

The compositions of the resin compositions of the respective examples are shown in Tables 1 to 3. In the table, the blending amounts of the components (B) to (E) or (B') to (E') are each a part by mass based on 100 parts by mass of the component (A) or the component (A').

The components used in this embodiment are as follows.

[Ring olefin homopolymer (A) with a glass transition temperature of 101 to 160 ° C]

A-1: a cyclic olefin homopolymer, manufactured by Zeon Co., Ltd., trade name "ZEONOR (registered trademark) 1420R", and a Tg of 135 °C.

A-2: a cyclic olefin homopolymer, manufactured by Zeon Co., Ltd., trade name "ZEONOR (registered trademark) 1020R", and a Tg of 102 °C.

[Comparative component (A') of component (A)]

A'-1: a cyclic olefin homopolymer, manufactured by Zeon Co., Ltd., trade name "ZEONOR (registered trademark) 1060R", and a Tg of 100 °C.

A'-2: a cyclic olefin homopolymer, manufactured by Zeon Co., Ltd., trade name "ZEONOR (registered trademark) 1600", and a Tg of 163 °C.

A'-3: a cyclic olefin copolymer, manufactured by Mitsui Chemicals Co., Ltd., trade name "APEL (registered trademark) 5014DP", and a Tg of 135 °C.

[Fibrous conductive filler (B)]

B-1: Carbon fiber, manufactured by Nippon Polymer Co., Ltd., trade name "EPU-LCL". Fiber diameter is 7.0μm, fiber length is 6.0mm (aspect ratio) Department 857).

[Comparative component (B') of [(B) component]

B'-1: A particulate conductive filler (the same as E-1 described below) was used.

[at least one type of elastomer (C) selected from the group consisting of an olefin-based elastomer and a styrene-based elastomer]

C-1: a styrene-based elastomer, manufactured by Asahi Kasei Chemicals Co., Ltd., trade name "Tuftec (registered trademark) H1053".

C-2: an olefin-based elastomer, manufactured by Mitsui Chemicals, Inc., under the trade name "TAFMER (registered trademark) A4085S".

[Comparative component (C') of [(C) component]

C'-1: a polyester elastomer, manufactured by Toyobo Co., Ltd., trade name "Pelprene (registered trademark) P150M".

[Polyethylene (D) with a viscosity average molecular weight of 1 million or more]

D-1: Ultrahigh molecular weight polyethylene, manufactured by Mitsui Chemicals, Inc., under the trade name "MIPELON (registered trademark) XM-220"; viscosity average molecular weight of 2 million and average particle diameter of 30 μm.

[Comparative component (D') of [(D) component]

D'-1: polyethylene (high-density polyethylene) having a viscosity average molecular weight of less than 1,000,000, manufactured by Preman Polymer Co., Ltd., trade name "HI-ZEX (registered trademark) 2208J"; viscosity average molecular weight of about 65,000 .

[Particulate conductive filler (E)]

E-1: carbon black, manufactured by Lion King Co., Ltd., trade name "Ketchen black (registered trademark) EC300J"; particle size (primary particle size) of 40 nm, aspect ratio of about 1, di-n-butyl phthalate (DBP) oil absorption is 360mL/100g.

[Comparative component (E') of [(E) component]

E'-1: carbon black, manufactured by Denki Kogyo Co., Ltd., trade name "Denka black (registered trademark)"; particle size (primary particle size) of 43 nm, di-n-butyl phthalate (DBP) oil absorption The amount is 165 mL / 100 g.

<Production Example of Resin Composition>

Each of the resin compositions (columnar pellets) of each example was produced by the following production methods according to the compositions (mixed components, blending amounts (parts by mass)) shown in Tables 1 to 3.

In the table, when there is a mixed column of the blank column, the blended component is not blended. The blending amount represents the pure component of the blended component.

(Example 1)

Using a twin-screw extruder NR-II (manufactured by NAKATANI KIKAI CO., LTD., screw diameter: 57 mm), the premixed mixture of the components (A) and (C) was previously used as the raw material of the extruder. When the mixture was completely melted at 280 ° C, the component (B) was forcibly supplied to the extruder through a side feeder by a dose feeder and kneaded, thereby obtaining a composite.

Next, after cooling the composite, a cylindrical pellet (2 mm in diameter and 2 to 4 mm in length) was prepared using a granulator (GF5, manufactured by Nakagawa Machinery Co., Ltd.).

(Examples 2 to 5)

The cylindrical pellets were prepared in the same manner as in Example 1 except that the composition shown in Table 1 was changed.

(Examples 6, 7)

Use twin screw extruder NR-II (made by Zhonggu Machinery Co., Ltd., screw diameter) 57mm), a premixed mixture of (A) component, (C) component and (D) component, which is supplied by the original hopper of the extruder, and when the mixture is completely melted, (B) The ingredients are forcibly supplied to the aforementioned extruder by kneading through a side feeder and kneaded, thereby obtaining a composite.

Next, this composite was cooled, and the same procedure as in Example 1 was carried out to prepare cylindrical pellets.

(Example 8)

A cylindrical pellet was prepared in the same manner as in Example 6 except that the component (D) was changed to the comparative component (D').

(Examples 9, 10)

The cylindrical pellets were prepared in the same manner as in Example 1 except that the components (B) and (E) were supplied together by a side feeder by a doser.

(Example 11)

The cylindrical pellets were prepared in the same manner as in Examples 6 and 7 except that the components (B) and (E) were supplied together by a side feeder by a doser.

(Embodiment 12)

The cylindrical pellets were prepared in the same manner as in Examples 9 and 10 except that the component (E) was changed to the comparative component (E').

(Comparative Example 1)

The component (C) was not blended, that is, the mixture was prepared in the same manner as in Example 1 except that the mixture of the component (A) and the component (C) which were previously premixed was changed to the component (A). grain.

(Comparative Example 2)

Do not blend (B) component, ie, use twin screw extruder NR-II (Zhonggu machine The screw system has a screw diameter of 57 mm. The premixed mixture of the component (A) and the component (C) is supplied by the original hopper of the extruder, and the composite is obtained by melt kneading.

Next, this composite was cooled, and the same procedure as in Example 1 was carried out to prepare cylindrical pellets.

(Comparative Example 3)

The cylindrical pellets were prepared in the same manner as in Example 1 except that the composition shown in Table 1 was changed.

(Comparative Example 4)

A cylindrical pellet was prepared in the same manner as in Example 2 except that the component (C) was changed to the comparative component (C').

(Comparative Example 5)

A cylindrical pellet was prepared in the same manner as in Example 2 except that the component (B) was changed to the comparative component (B').

(Comparative examples 6 to 8)

A cylindrical pellet was prepared in the same manner as in Example 1 except that the component (A) was changed to the comparative component (A').

<Evaluation of Resin Composition>

With respect to the resin composition of each example, the mechanical strength, the electrical conductivity, the outgassing property, the abrasion resistance, the fusion bondability, and the electrical conductivity are stabilized by the evaluation methods described below, and the formation due to the molding is suppressed. The effect of body warping was evaluated.

Production of test strips:

Injection molding machine (made by Nissei Resin Industrial Co., Ltd., FS120EM25ASE), a dumbbell-shaped test piece for strength measurement (multi-purpose test piece A of ISO standard), and conductivity measurement by a conventional resin composition (columnar pellet) prepared by the above-mentioned production example A flat plate (76 mm × 76 mm × 3.2 mm) and a test piece (310 mm × 360 mm × 20 mm) for evaluating the warpage of the molded body were used to prepare a test piece for each evaluation. The forming temperature is set to 250 to 280 ° C and the mold temperature is set to 50 ° C.

[Mechanical strength]

The flexural strength and the Charpy impact strength were measured as the indexes of the mechanical strength according to the methods shown below.

‧Bending strength

The flexural strength is determined by the method according to ISO 178/A/2. When the bending strength exceeds 80 MPa, it is qualified.

‧Salpi impact strength

The Charpy impact strength is determined by the method according to ISO 179/1eA. When the Charpy impact strength exceeds 3.0 kJ/m ² , it is qualified. The greater the value of the aforementioned Charpy impact strength, the better the impact resistance.

[heat resistance]

The load deformation temperature (HDT) was measured as an index of heat resistance by the method according to ISO 75-2Af. When the load deformation temperature is 95 ° C or higher, it is qualified. The higher the load deformation temperature, the better the heat resistance.

[Electrical conductivity]

The surface resistivity was measured as an index of conductivity by the method according to ASTM D257. When the surface resistivity is 1.0E+4~1.0E+10 (1.0×10 ⁴ ~1.0×10 ¹⁰ )Ω, it is qualified.

[Low outgassing]

The amount of outgas production was measured according to the method shown below as an indicator of low outgassing.

Weigh 5.0 g of each of the resin compositions (cylindrical pellets) and take them to a test tube, which was measured by a headspace (HS) method using a gas chromatography mass spectrometer (GC-MS) at 150 ° C. The amount of outgas generated when heated for 1 hour.

The amount of volatile gas to be produced, converted from the relative concentration of phenol used, is calculated as the amount of outgas generated in terms of the concentration per unit mass.

For the measurement device, 5890 manufactured by HP Corporation was used as a gas chromatograph, and 5972 manufactured by HP Corporation was used as a mass spectrometer.

When this outgas production amount is less than 40 ppm, it is qualified. The smaller the amount of outgassing, the more excellent the low outgassing property.

[wear resistance]

The wafer sliding load was measured by a wafer sliding abrasion test as an index of wear resistance.

On the platform, the washed/dried injection-molded test piece (20 mm × 40 mm × 3 mm) was brought into contact with the outer peripheral portion (peripheral surface) of the silicon wafer having a diameter of 300 mm, and an amplitude tester was used to carry out 100,000 amplitudes. 2mm round trip test.

After the completion of the round-trip test, the amplitude tester was removed, and the peripheral surface of the tantalum wafer which was brought into contact with the injection-molded test piece was connected to a tensile tester positioned vertically upward by a pulley. Then, the tensile load is measured at a fixed speed, and the value is the wafer sliding load (N). For the tensile tester, Tensiron RTC-1325A (manufactured by ORIENTEC) was used.

When the sliding load of the wafer is within 0.40N, it is better, and is A, when it is more than 0.40 and within 0.60N, it is good, and when it is more than 0.60N, it is bad, and it is C. The abrasion resistance was evaluated.

[welding joint]

When a cubic-shaped container (width: 430 mm × length: 356 mm × height: 339 mm) was produced by one-shot injection molding, the state of generation of a wire (melt line) generated in a portion where the resin composition in a molten state merged was observed by visual observation. (Appearance of the aforementioned container) to evaluate the weldability.

Then, the condition of the weld line is not observed to be substantially A, and the condition of the weld line is slightly observed to be B, and the condition generated by the weld line is clearly observed as C, to weld the joint. Conduct an evaluation.

[Electrically Conductive Stability]

The standard deviation (deformity) of the surface resistivity was obtained as an indicator of the stabilization of conductivity (antistatic efficiency).

A flat disk (76 mm × 76 mm × 3.2 mm) for measuring conductivity was divided into six zones, and the surface resistivity of each zone was measured. The surface resistivity was measured by using MCP-HT260 Hiresta IP manufactured by Mitsubishi Chemical Analysis Co., Ltd., and measured by an electrode shape URS probe.

Calculate the common logarithm of the surface resistivity of each zone and analyze the standard deviation (parallel).

When the surface resistivity is less than 0.03 in the standard deviation of the common logarithm, the conductivity stability is good and A is made, and when it is 0.03 or more and less than 0.10, the conductivity stability is good and B is obtained, and when it is 0.10 or more Conductive stability was evaluated for the conductivity difference and C.

[Effect of suppressing warpage of a molded body due to molding]

The injection-molded test piece (310 mm × 360 mm × 20 mm) was placed on a horizontal table, and the distance between the end portion of the longitudinal direction (direction parallel to the side of 360 mm) and the stage was measured. Then, the maximum value of the distance (the distance L between the end portion of the stage and the stage) is "the amount of warpage of the molded body", and the effect of suppressing the warpage of the molded body due to the molding is performed. Evaluation.

When the amount of warpage (interval distance L) of the molded body is less than 0.10 mm, the effect of suppressing warpage is good, and A is good, and when it is 0.10 mm or more and less than 0.20 mm, the warp suppression system is good. In the case of B, when it is 0.20 mm or more, the warp is not suppressed and C is determined, and the effect of suppressing warpage of the molded body is evaluated.

From the results shown in Tables 1 to 3, it is understood that the resin composition according to the embodiment to which the present invention is applied is excellent in any of mechanical strength, heat resistance, electrical conductivity, and low outgassing property when the molded article is produced.

From the results shown in Table 2, it is understood that by further containing the component (D) in addition to the components (A) to (C), the wear resistance and fusion of the wafer and the like are further improved. Follow-up.

As a result of the results shown in Table 3, by further containing the component (E) in addition to the components (A) to (C), it is possible to further stabilize the conductivity. Further, it has been found that when the ratio of the component (B) to the component (E) is 3.0 or less, the effect of the warpage suppressing effect is high.

From the comparison between Example 9 and Example 12, it was found that Example 9 containing E-1 having a DBP oil absorption of 180 mL or more was compared with Example 12 containing E'-1 having a DBP oil absorption of less than 180 mL, although When the amount of the particulate conductive filler is small, it exhibits the same conductivity, and the electrical conductivity is stabilized and the warpage of the molded body due to the molding is suppressed.

Industrial availability

The resin composition according to the present invention can provide a molded article excellent in any of mechanical strength, heat resistance, electrical conductivity, and low outgassing property.

Claims (4)

A resin composition comprising: a cyclic olefin homopolymer (A) having a glass transition temperature of 101 to 160 ° C, a fibrous conductive filler (B), and a olefin-based elastomer and benzene selected from the group consisting of At least one type of the elastomer (C) in the group of the ethylene-based elastomers; and the content of the elastomer (C) is 5 to 25 parts by mass based on 100 parts by mass of the cyclic olefin-based polymer (A). The resin composition of claim 1 further comprising polyethylene (D) having a viscosity average molecular weight of 1,000,000 or more. The resin composition according to claim 1 or 2, further comprising a particulate conductive filler (E). The resin composition according to claim 3, wherein the particulate conductive filler (E) is a carbon black having a di n-butyl phthalate oil absorption of 180 mL/100 g or more.