JPH01259052A - Antistatic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, having lasting antistatic effects and suitable for packaging and packing related to semiconductors, packaging electronic circuit boards, etc., by blending a specific ethylenic random copolymer with a high polymer charge-transfer type conjugate. CONSTITUTION:A composition obtained by blending (A) 100pts.wt. ethylenic random copolymer, consisting of 99-75wt.% ethylene and 1-25wt.% 4-10C alpha-olefin and having 0.91-0.94g/cm<3> density and 0.1-50g/10min melt flow rate with (B) 0.01-10pts.wt. high polymer charge-transfer type conjugate prepared by reacting (B1) a semipolar organoboron high polymer expressed by formula I [q is 0 or 1; A is -(X)a-(Y)b-(Z)c- (X and Z are <=100C oxygen-containing hydrocarbon having one terminal ether residue; Y is formula II (R is 1-82C hydrocarbon group), etc.; a-c are 0 or 1; p is 10-1,000] with (B2) a 5-82C tertiary amine having >=1 hydroxyl groups at a ratio of one boron atom to one basic nitrogen atom.

Description

[Detailed Description of the Invention] [Background of the Invention] (Industrial Application Field) The present invention is applicable to semiconductor-related packaging and packaging, electronic circuit board packaging, electronic component packaging, electronic equipment, medical equipment,
The field of packaging and covers for precision equipment, etc. relates to resin compositions for preventing electrostatic damage, intended for use in dust-proof packaging for pharmaceuticals, cosmetics, food products, packaging for hazardous materials, etc.

(Prior art and problems to be solved by the invention) Plastics are used in a wide range of fields because they have excellent properties such as transparency, durability, and lightness.
Since this is an electrically insulating material, various problems may occur due to static electricity depending on the usage or application.

In particular, in the electronics field, ICs that use static electricity.

The destruction and damage of LSIs has become a problem, and countermeasures against static electricity are an important and urgent topic.

To do this, it is necessary to improve the electrical properties of the surrounding insulating materials themselves, which tend to generate pre-static charges.
Films and sheets containing carbon black, graphite, tin oxide, zinc oxide, indium oxide, etc. have been made. However, unless these inorganic conductive agents are mixed into the matrix resin in such a large amount that they come into contact with each other, it is impossible to transform the material into a material that is not electrically charged as a whole, which increases costs and significantly impairs the physical properties of the base material. It had the disadvantage of being subject to change. Another drawback was that transparent antistatic molded products could not be made using these inorganic materials.

In this sense, internally kneaded antistatic agents using surfactants only need to be added in a small amount, do not change the physical properties of the base material too drastically, and can be used to make transparent molded products. Since it can be processed easily and at low cost, it has been widely used as a countermeasure against static electricity, mainly aimed at preventing the adhesion of dust.

However, antistatic agents only become effective when the molecules migrate to the surface of the base material, and what is on the surface is unstable and may be affected by external conditions and factors such as temperature, humidity, contact, and friction. It is disturbed and removed, and most of the molecules inside migrate to the surface and are removed after a certain period of time, so it is not possible to provide stability and sustainability of the effect. There wasn't.

Furthermore, since the antistatic mechanism itself is based on the carrier effect (ion conduction mechanism) brought about by the hydrophilic group portion of the antistatic agent molecules present on the surface, even the slightest disturbance in the orientation and adsorption state of the antistatic agent molecules on the surface When this occurs, it becomes impossible to attenuate 100% before charging.

Therefore, in a strict sense, antistatic agents cannot be said to be a means for eliminating the influence of surrounding static electricity during transportation, use, etc. of IC and LSI-related functional products.

[Summary of the invention]

(Means for Solving the Problems) The present invention provides a solution to this problem, and uses a specific ethylene random copolymer that maintains a semipolar bond structure and has boron atoms arranged in a regular manner within the molecule. By combining a polymeric charge transfer type bond produced by reacting an incorporated organoboron polymer compound with a hydroxyalkylamine, the electrostatic property of the ethylene copolymer is removed, and the ethylene copolymer is free from contact, friction, The present invention was completed based on the discovery that the pre-static charge that occurs instantaneously due to the application of an external voltage, etc. is quickly and completely leaked, and that unlike the above-mentioned antistatic agents, it is possible to create permanent and stable static-free products. did.

Summary: The antistatic resin composition according to the present invention comprises the following components (1) and (2).

Component (1): Density is 0.910 to 0.940 g/cI
Ij1 melt flow rate is 0.1 to 50 g/10 minutes, and ethylene is 99 to 75% by weight and carbon number is 4 to 1
An ethylene random copolymer comprising 1 to 25% by weight of α-olefin of 0 and 1 to 25% by weight.

Component (2): one type of semipolar organic boron polymer compound represented by the following general formula I or 2Fff or more and a total carbon number of 5 to 8 having at least one hydroxyl group
A polymer charge transfer type conjugate (hereinafter referred to as a predetermined polymer charge transfer type conjugate) which is a reaction product of one boron atom to one basic nitrogen atom with one or more types of tertiary amines (2). (referred to as a type combination).

[In the formula, q is 0 or 1, and when q-1, A is -(X)
a-(Y) b-(Z) c- group (wherein, X and Z are oxygen-containing hydrocarbon groups having a total of 100 or less carbon atoms with one terminal ether residue; a, b.

C is O or 1. ), and p is 10 to 1000
It is. ] Effect The antistatic resin composition according to the present invention has such a permanent antistatic effect that it can be called a permanent antistatic resin composition.

That is, the predetermined polymeric charge transfer type conjugate of the present invention used in the above-mentioned specific ethylene random copolymer is a coordinate bond type ionic structure substance, and even though it is a highly polar polymeric substance, However, since it melts and mixes well with the ethylene copolymer, which has low polarity, it is not expelled from the base resin and acts as a foreign material forming a Fermi level, so it only neutralizes the direction of charge on the surface. Unlike the case of antistatic agents, which are statically charged, we not only make the base resin a permanently non-static material from within under normal conditions, but also it remains constant even after repeated forced charging under high voltage.
00% charge can be leaked. Furthermore, the predetermined polymer charge transfer type conjugate of the present invention is a conductive polymer exhibiting electron mobility.

Therefore, since it exhibits electronic conductivity, unlike an antistatic agent based on an ionic conduction mechanism, it exhibits a sufficient antistatic effect even if it is not present on the surface of the base material.

Furthermore, since the predetermined polymeric charge transfer type conjugate of the present invention has extremely good thermal stability, a resin composition containing the same hardly exhibits any decrease in physical properties due to thermal deterioration even when handled at high molding temperatures. I can't watch it.

[Detailed description of the invention]

Definition The antistatic resin composition according to the present invention comprises component (1) and component (2).

Here, "comprising" means that in addition to these two essential components, auxiliary materials (details will be described later) may be included as long as they do not impair the spirit of the present invention.

Component (1) The ethylene copolymer used in the present invention is composed of ethylene and α-
It is a random copolymer consisting of olefin.

The α-olefins having 4 to 10 carbon atoms constituting the ethylene random copolymer used as component (1) include butene-1, pentene-1, hexene-1,4-methylpentene-1, octene-1, and decene. -1, etc., and these can also be used in combination. Ingredients in the present invention (1
) is composed of 99 to 75% by weight of ethylene and 1 to 25% by weight of C4 to C1o α-olefin, but if necessary, a smaller amount of a third monomer than this α-olefin is copolymerized. There may be.

Note that the contents of ethylene and α-olefin are based on the contents of both.

The density of the copolymer is 0.910 to 0.940 g/cil,
Preferably it is 0.915 to 0.930 g/cIIl. If the density is less than 0.910, the heat sealing strength is poor and it tends to become sticky, so when it is made into a film product, blocking etc. may occur, which is not preferable.

Furthermore, if the density exceeds 0.940, the high-performance antistatic effect that is the object of the present invention cannot be obtained. In order for the density of the copolymer to be within the above range, the amount of α-olefin component must be 1 to 1.
It is usually in the range of 25 to 10% by weight, preferably 2 to 10% by weight.

The melt flow rate of the copolymer is 0.1-50g/10
minutes, preferably 1 to 25/10 minutes, more preferably 5
~20 minutes/10 minutes. If the melt flow rate is below the above range, the fluidity will be poor and the processability will be poor, and if it is above the above range, the heat sealability and material strength will deteriorate, which is not preferable.

Such an ethylene random copolymer can be produced by any suitable production method. for example,
As a catalyst, a transition metal oxide catalyst such as a chromium oxide catalyst using silica or alumina as a carrier, a transition metal halide of groups 1 to 2 such as titanium halide or vanadium halide, and an alkylaluminium-magnesium complex, Using a coordination catalyst consisting of a combination with an organometallic compound of Groups 1 to M, such as an organoaluminum-magnesium complex such as an alkyl alkoxyaluminum-magnesium complex, or an organoaluminum such as an alkyl aluminum or an alkyl aluminum chloride, Suspension polymerization, solution polymerization, gas phase polymerization and 1000-3
It is manufactured by various processes such as high-pressure polymerization in which polymerization is carried out at 150 to 300°C at 1,000 atmospheres.

Component (2) The predetermined polymeric charge transfer type conjugate used as an antistatic material in the present invention is a combination of one or more semipolar organic boron polymer compounds of formula (1) and a hydroxyl group-containing tertiary compound. It is a reaction product with one or more amines (provided the ratio is one boron atom to one basic nitrogen atom).

The former boron compound of formula (I) is, for example, the following (a
) or (b).

(a) Modulus formula■ [In the formula, q is O or 1, and when q-1, A is -(X)
a-(Y) b-(Z) c- group (wherein X and Z are carbon dispersions with one terminal ether residue: l 100 or less oxygen-containing hydrocarbon groups, Y is 82, preferably 6 to 82, hydrocarbon group) if R' has 2 to 13 carbon atoms, preferably 6
~13, hydrocarbon group), and aSb and C are each 0 or 1. )] per 1 mole of one or more compounds represented by 1 mole of boric acid or a boric acid triester of a lower alcohol having 4 or less carbon atoms, or 0 boric anhydride. Triesterification reaction is carried out by reacting .5 mol.

(b) Total number of carbon atoms including di(glycerol)-borate or di(glycerol)-borate residue in the middle: 20
6 or less, preferably 10 to 100, one type or two or more types of diols are subjected to a polyetherification reaction, or
Or a dicarboxylic acid having 3 to 84 carbon atoms, preferably 8 to 84 carbon atoms (hereinafter referred to as a predetermined dicarboxylic acid), or a dicarboxylic acid having 4 or less carbon atoms, or a dicarboxylic acid having 3 to 84 carbon atoms, preferably 8 to 84 carbon atoms, or One type of ester of a lower alcohol and a predetermined dicarboxylic acid, a halide of a predetermined dicarboxylic acid, or a diisocyanate having 4 to 15 carbon atoms, preferably 8 to 15 carbon atoms (hereinafter referred to as the predetermined diisocyanate); A total of 1 mol of two or more species is reacted.

One or more semipolar organic boron polymer compounds produced in this way (hereinafter referred to as predetermined semipolar organic boron polymer compounds) and at least one hydroxyl group having a total carbon number of 5 to 5. 82, preferably 5
-30, one type or two or more types of secondary amines (hereinafter referred to as predetermined tertiary amines) in a ratio designed to be one boron atom to one basic nitrogen atom, Pour into a closed or open reactor, under normal pressure, 20~2
If the reaction is carried out at 00°C, preferably 50 to 150°C, the antistatic agent of the present invention (hereinafter referred to as a predetermined polymeric charge transfer type conjugate) is produced. At this time, the reaction can be carried out more easily if a polar solvent such as alcohol, ether, or ketone is present.

The raw materials for deriving the predetermined polymer charge transfer type conjugate of the present invention and the predetermined semipolar organic boron polymer compound which is an intermediate thereof are as follows.

First, a given semipolar organic boron polymer compound is derived (
Examples of the compounds represented by the maximum number ■ that are the raw materials for the method a) include diglycerin, di(glycerin)-malonate, di(glycerin)-maleate, and di(glycerin).
-Adipart, di(glycerin)-terephthalate, di(glycerin)-dodecanate, poly(9 mole)oxyethylene di(glycerin ether), di(glycerin)-tolylene dicarbamate, di(glycerin)-methylenebis(4- On the other hand, the predetermined dicarboxylic acids in method (b) include, for example, malonic acid, maleic acid, succinic acid,
Dimer acids derived from adipic acid, sebacic acid, phthalic acid, terephthalic acid, dodecane dioic acid, linoleic acid,
Examples include dodecyl maleic acid, dodecenyl maleic acid, octadecyl maleic acid, octadecenyl maleic acid, and maleic acid in which polybutenyl groups with an average degree of polymerization of 20 are linked. ,
Examples include ethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, and methylene bis(4-phenylisocyanate).

Next, examples of the predetermined tertiary amine to be reacted with the predetermined semipolar H-organic boron polymer compound include diethyl-hydroxymethylamine 2-bitroxyprobylamine, methyldi(2-hydroxyethyl-amine, tri( 2-hydroxyethyl)
Ethylene oxide (1-
25 mol) adduct, and a propylene oxide (1 to 26 mol) adduct of monobutylamine.

In connection with the present invention, when the amine raw material to be reacted with a predetermined semipolar organic boron polymer compound is of a type other than the predetermined tertiary amine, that is, a -class or secondary amine, a charge transfer type bond is used. The body is not built properly, and
Since the resulting compound also becomes an unstable compound, it is difficult to develop and maintain electrical conductivity, and therefore permanent antistatic properties cannot be imparted to the ethylene random copolymer.

Furthermore, when using a tertiary amine that does not have a hydroxyl group, it is not possible to connect the generated polymeric charge transfer type conjugates through multiple hydrogen bonds, and therefore the mobility of individual chains is reduced. This is not preferable because it causes a change in the aggregation state in the base material, resulting in insufficient charge leakage.

Composition of the Present Invention The amount of the predetermined polymeric charge transfer type binder of the present invention added to the ethylene random copolymer varies depending on the purpose, but is generally 0.01 parts by weight per 100 parts by weight of the copolymer. ~1
0 parts by weight, preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight. If the amount is too small, high-performance antistatic properties, which is the object of the present invention, cannot be obtained. On the other hand, if the amount is too large, problems such as coloring and bleeding may occur, which is not preferable.

The resin composition of the present invention may optionally contain an inorganic filler,
Organic fillers, other polyolefin resins different from the ethylene random copolymer of the present invention, polymer materials such as elastomers may be blended within a range that does not impair the effects of the present invention to improve processability, rigidity, flexibility, etc. can. The above polymeric materials are preferably incorporated in amounts up to 50% by weight of the composition of the invention.

In addition to the above ingredients, other compounding agents such as stabilizers, antioxidants, lubricants, processing aids such as anti-blocking agents, flame retardants, various pigments, dyes, ultraviolet absorbers, etc. are of course used as appropriate. It is possible.

The resin composition of the present invention can be produced by any conventionally known compounding method.

For example, as the cross-contact method, an open roll, intensive kneader, co-kneader, single-screw or twin-screw extruder, etc. are used.

As a specific example, the ethylene random copolymer of the present invention in powder or pellet form is blended with a predetermined polymeric charge transfer type conjugate and desired additional components, mixed with a Henschel mixer, etc. The mixture is melt-mixed in a twin-screw extruder to form a pellet-like composition. The compounding components may be added to the resin during mixing, or may be added in a masterbatch method.

The obtained pellets are subjected to injection molding, extrusion molding, blow molding,
The molded product is subjected to various molding processes such as air pressure molding, film molding, hot pressure molding, and spinning, and is further subjected to secondary processing as necessary to obtain a molded product.

For extrusion molding, blow molding, etc. of films and sheets,
Multilayering with other resins is also possible, and depending on the purpose, the resin composition of the present invention can be used as a surface layer on one side or as a surface layer on both sides. Furthermore, a layer of the resin composition of the present invention can be formed on the surface of a molded article made of a resin containing metal, metal oxide, or carbon-based conductive filler.

These molded bodies are used in many fields for the purpose of preventing static electricity and removing static electricity. For example, in the case of anti-static, IC
Applicable to transportation and storage packaging materials (carriers, trays, bags, racks, containers, etc.), parts boxes for electronic components, cases for magnetic tapes, audio tapes, slip sheets, and packaging materials for hazardous materials such as explosives. Furthermore, it can be applied to static electricity removal rolls, sheets, etc., and as a semiconductor material, it can be applied to information recording paper, various resistors, etc.

In addition, with respect to the resin composition of the present invention, a powder or fiber of silver, copper, brass, iron, etc., or a conductive filler such as carbon black, tin-coated titanium oxide, tin-coated silica, etc. may be coexisting. The resulting molded product becomes a more precise electromagnetic shielding material.

Furthermore, when the resin composition of the present invention is made into a film, it has good water wettability and is therefore suitable as an agricultural house material or a packaging material for frozen foods.

[Examples, etc.]

Examples will be given below to further explain in detail. In these examples, "parts" mean parts by weight, and "%" mean % by weight.

Further, the predetermined polymer charge transfer type conjugate used in each example consists of a predetermined polymer charge transfer type conjugate having the structural formula shown in Table 1 below.

Example 1 The present invention was applied to 100 parts of ethylene-butene-1 random copolymer (butene-1 content ff 1-8%, density - 0,920 g/CI!, melt flow rate - 2,0 g/10 min) An appropriate amount of each of the predetermined polymeric charge transfer type conjugates was added thereto, and the mixture was melt-kneaded at 190°C in a single-screw extruder to obtain pellets. The pellets were molded into a sheet at 200° C. to obtain a sheet with a thickness of 150 μm. After that, the sheet was kept under constant temperature and humidity conditions of 23°C and 50% RH for 3 days.
Let it stand for 0 days, and measure the surface resistivity and charge attenuation rate (however,
After applying a voltage of 10 KV to the sample surface to forcibly charge it, the voltage was removed and the presence or absence of residual charge was checked 2 minutes later and converted. ) was measured. For comparison, N,N-di(2-hydroxyethyl)stearylamine, a known antistatic agent, was selected and subjected to the same test.

Here, a specific method for producing the predetermined polymer charge transfer type conjugate used in this example will be shown for example, for the predetermined polymer charge transfer type conjugate (1) and (2).
It is as follows.

That is, the predetermined polymeric charge transfer type conjugate (1) is prepared by charging 1 mole of di(glycerin) bollard and 1 mole of adipic acid to a four-way flask equipped with a stirring bar, a thermometer, an N2 gas inflow tube, and a water sample tube. , under N2 gas inflow, 220~2
It takes 4 hours at 30°C to react until 2 moles of dehydration is obtained, and after confirming an increase in melt viscosity, it is cooled to 70°C.

After that, the same amount of methyl ethyl ketone as the product was injected to make a homogeneous solution, and then 1 mole of poly(25 mol) oxyethylene-dihexadecylamine was added.
React at 70-75°C for an hour, then at 150mmH.
It is obtained by distilling the diluent solvent methyl ethyl ketone out of the system over a period of 2 hours at 120 to 130° C. under a reduced pressure of 1.5 g.

Further, the predetermined polymeric charge transfer type conjugate (5) is poly(
9 mol) oxyethylene di(glycerin ether) 1
Prepare 1 mol of boric acid and 1 mol of boric acid, under N2 gas flow,
It takes 5 hours at 30°C to react until 3 moles of dehydration is obtained, and after confirming an increase in melt viscosity, it is cooled to 70°C. After that, the same amount of isopropyl alcohol as the product was injected to make a homogeneous solution. Then, 1 mole of behenyludi(2-hydroxyphenethyl)amine was added and reacted at 75 to 80°C for 1 hour. By distilling the diluting solvent, isopropyl alcohol, out of the system over a period of 3 hours at 150 to 160°C under normal pressure.
That's what you get. Incidentally, the method for producing other predetermined polymeric electron-4I transfer type conjugates is also the same as the method described above.

The test results are shown in Table 2, and the ethylene random copolymer sheet in which the specified polymeric charge transfer type conjugate of the present invention was homogeneously dispersed did not leave any charge, and the performance deteriorated over time. It turns out that this phenomenon is almost never observed.

Example 2 Ethylene-octene-1 random copolymer (octene-1
1-6%, density -0.92'5g/crd.

To 100 parts of melt flow rate (4.0 g/10 min), appropriate amounts of the predetermined polymeric charge transfer type conjugate of the present invention, an anti-blocking agent, and a slip agent were added, and the mixture was heated at 200°C in a single-screw extruder. The pellets were melted and kneaded to obtain a beret. Using the pellet, film molding was performed at 220° C. using a T-die extruder to obtain a film with a thickness of 50 μm. Regarding the electrical properties of these films, i'11J was determined in the same manner as in Example 1.

For comparison, low-density homopolyethylene produced by high-pressure polymerization method (density - 0,920 g/c! II, melt flow rate - 4,0 g/10 min, and density - 〇, 925 g
/cm3, melt flow rate -4.0 g/10 minutes).

The test results are shown in Table 3, and it was found that the composition of the present invention had superior electrical properties compared to the low density polyethylene base of the comparative example, despite having the same density.

Example 3 Same as Example 2 except that ethylene-butene-1 random copolymer (butene-1 content - 8%, density - 0,930 g/ctr1, melt flow rate - 1,5 g/10 min) was used. Electrical characteristics were evaluated using the same method. For comparison, high-density polyethylene (density -0,950
g/cnl, melt flow rate -1.0 g/10 min)
A similar test was conducted using

The test results are shown in Table 4, and it was confirmed that the film made of the composition of the present invention did not leave any charge and had stable electrical properties over time. On the other hand, in the comparative system, charge attenuation was insufficient and the desired performance of the present invention could not be obtained.

Example 4 Using the composition of Example 1 and the ethylene-butene-1 random copolymer as the base resin of Example 1, tie-lamination molding was performed at 200°C with a multilayer sheet molding machine, and the present invention composition / ethylene-butene-1 random copolymer / composition of the present invention (thickness is 100/250/
A sheet having a three-layer structure with a thickness of 100 μm) was produced. The electrical properties of the multilayer sheet were measured in the same manner as in Example 1.

For comparison, N,N-di(2-
Hydroxyethyl) stearylamine was selected and subjected to similar tests.

The test results are shown in Table 5, and it was confirmed that the electrical properties of the multilayer sheet having the composition of the present invention formed on the surface layer showed almost no deterioration in performance over time as in the comparative example.

Procedural amendment 1 Indication of the case 1988 Patent application No. 85780 2 Name of the invention (605) Mitsubishi Yuka Co., Ltd. (and 1 other person) 4 Column 8 of "Detailed description of the invention" in the agent's specification 8 Amendment Contents (1) 1 table shown on pages 28 to 34 of the specification
Correct IJ as shown below.

Table 1

Claims (1)

[Scope of Claims] An antistatic resin composition comprising the following components (1) and (2). Component (1): Density is 0.910 to 0.940 g/cm^
3. Melt flow rate is 0.1 to 50 g/10 minutes, and ethylene is 99 to 75% by weight and carbon number is 4 to 10
An ethylene random copolymer comprising 1 to 25% by weight of α-olefin. Component (2): One or more semipolar organic boron polymer compounds represented by the following general formula I and a total carbon number of 5 to 82 having at least one hydroxyl group.
A polymeric charge transfer type conjugate which is a reaction product of one boron atom to one basic nitrogen atom with one or more tertiary amines. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... I [In the formula, q is 0 or 1, and when q=1, A is -(X)
a-(Y) b-(Z) c- group {However, X and Z are oxygen-containing hydrocarbon groups having a total of 100 or less carbon atoms with one terminal ether residue, Y is ▲ mathematical formula, chemical formula, table, etc. There is a ▼ group (where R is a hydrocarbon group having 1 to 82 carbon atoms) or a ▲ mathematical formula, chemical formula, table, etc. ▼ group (where R' is a hydrocarbon group having 2 to 13 carbon atoms), a, b, and c are each 0 or 1. }, and p is 10~
It is 1000. ]