JP2654078B2 - Antistatic resin composition - Google Patents

Description

BACKGROUND OF THE INVENTION (Industrial Application Field) The present invention relates to semiconductor-related packaging and packaging, electronic circuit board packaging, electronic component packaging, electronic equipment, medical equipment, precision equipment and the like. The present invention relates to a resin composition for countermeasures against static electricity, which is used for packaging and covers, dust-proof packaging of pharmaceuticals, cosmetics, and foodstuffs, packaging of dangerous goods, and the like.

[Problems to be solved by conventional technology and invention]

Plastics are used in a wide range of fields because of their excellent properties such as transparency, durability, and light weight.However, since these are electrically insulating materials, various obstacles due to static electricity may occur depending on the usage or application. This is a problem. In particular, in the electronics field, destruction and damage of ICs and LSIs due to static electricity have become a problem, and measures for static electricity are an important and urgent theme.

To do so, it is necessary to improve the electrical properties of the insulator material itself, which is likely to generate charged charges in the surroundings. Until now, plastics containing metal fibers, metal-plated fibers, etc., carbon black, graphite, oxidized Films and sheets containing tin, zinc oxide, indium oxide and the like have been produced. However, these inorganic conductive agents cannot be converted into a material that does not charge the whole unless they are mixed in a matrix resin in such a large amount that they come into contact with each other, which increases the cost and significantly increases the physical properties of the base material. There was a drawback of changing it. Also, it was difficult to produce a transparent antistatic molded article with these inorganic substances.

In that sense, the fact that the internal kneading type antistatic agent to which a surfactant is applied can be added in a small amount, does not significantly change the physical properties of the base material, and can produce a transparent molded article, Since it can be processed simply and at low cost, it has been widely used for antistatic measures mainly intended to prevent the adhesion of dust.

However, the effect of the antistatic agent is manifested only when the molecules migrate to the surface of the base material, and the one that appears on the surface is unstable and has a temperature, humidity or contact,
The stability of the effect is maintained because the internal molecules are disturbed or removed due to external conditions and factors such as friction, and most of the molecules inside move to the surface and escape after a certain time. Gender could not be given. Furthermore, since the antistatic mechanism itself is based on the carrier effect (ion conduction mechanism) provided by the hydrophilic group portion of the antistatic agent molecules present on the surface, the orientation and adsorption of the antistatic agent molecules on the surface are disturbed at all. Occurs,
It was impossible to attenuate the charge by 100%.

Therefore, it cannot be said in a strict sense that the antistatic agent is a means capable of eliminating the influence of the surrounding static electricity when transporting or using the IC and LSI-related functional products.

[Summary of the Invention]

(Means for Solving the Problems) The present invention provides a solution to this problem,
Polymer charge-transfer conjugate made by reacting vinylidene fluoride resin with an organic boron polymer compound in which boron atoms are regularly incorporated into the molecule and hydroxyalkylamine while maintaining a semipolar bonding structure By the combination of, the chargeability of the vinylidene fluoride resin is removed, contact, friction, the charge generated instantaneously by the application of an external voltage, etc. is quickly and completely leaked, and the above antistatic agent and On the contrary, they have found that a permanent and stable uncharged product can be produced, and the present invention has been completed.

SUMMARY That is, the antistatic resin composition according to the present invention comprises the following components (1) and (2).

Component (1): Vinylidene fluoride resin Component (2): One or more semipolar organoboron polymer compounds represented by the following general formula I, and a total carbon number of 5 having at least one hydroxyl group To 82 or more tertiary amines having a ratio of one boron atom to one basic nitrogen atom, a polymer charge transfer conjugate (hereinafter referred to as a predetermined polymer charge). It is referred to as a transferable conjugate.)

[Wherein, 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 one terminal ether residue and having a total of 100 or less carbon atoms, and Y is (Where R is a hydrocarbon group having 1 to 82 carbon atoms) or (Where R 'is a hydrocarbon group having 2 to 13 carbon atoms)
a, b, and c are 0 or 1. ｝ And p is
10 to 1000. Effect The antistatic resin composition according to the present invention has a permanent antistatic effect that can be called a permanent antistatic resin composition.

That is, the predetermined polymer charge-transfer conjugate of the present invention used in the vinylidene fluoride resin is a coordination bond type ionic structure substance, and although it is a polymer substance having a large polarity, it has a high polarity. It melts and mixes well with the vinylidene fluoride resin having a small particle size, so that it does not repel from the base resin and acts as a heterogeneous substance in the form of a Fermi level. Unlike the case of the agent, under normal conditions, not only can the base resin be permanently non-charging material from the inside, but also 100% charge can be constantly leaked even if repeated forced charging under high voltage is repeated it can. Further, the predetermined polymer charge-transfer conjugate of the present invention is a conductive polymer exhibiting electron mobility. Therefore, unlike an antistatic agent based on an ion conduction mechanism because of exhibiting electron conductivity, it exhibits a sufficient antistatic effect even when it does not exist on the surface of the base material.

In addition, since the predetermined polymer charge transfer type conjugate of the present invention has extremely good thermal stability, the resin composition containing the same hardly deteriorates in physical properties due to thermal degradation even at a high molding temperature. I can't see it.

(Specific description of the present 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 essential two components, auxiliary materials (details described later) may be included as long as the gist of the present invention is not impaired.

Component (1) The vinylidene fluoride resin used as the component (1) in the present invention is a homopolymer of vinylidene fluoride (hereinafter referred to as PVDF), and copolymerizable with at least 50 mol% of vinylidene fluoride. Copolymer with the remaining amount of the monomer. The monomer copolymerizable with vinylidene fluoride is not limited as long as it can be literally copolymerized with vinylidene fluoride, for example, ethylene, olefins such as propylene, vinyl chloride, chlorine-substituted vinyl compounds such as vinyl chloride, Fluorine-substituted olefins and the like are preferable, and especially fluorine-substituted olefins such as tetrafluoroethylene, vinyl fluoride, trifluoroethylene and propylene hexafluoride are preferable.

These vinylidene fluoride resins can be produced by any of known vinylidene fluoride polymerization methods such as emulsion polymerization and suspension polymerization.

In addition, the intrinsic viscosity ηi of these vinylidene fluoride resins
Is suitably in the range of 0.4 to 1.5, preferably 0.7 to 1.2. If the intrinsic viscosity ηi is less than 0.4, the strength of the obtained molded article is low, and if the intrinsic viscosity ηi exceeds 1.5, there is a problem in moldability unless other solvents, plasticizers and the like are used.

 Here, the intrinsic viscosity ηi refers to a value represented by the following equation.

η: Viscosity of a dimethylformamide solution of vinylidene fluoride resin having a concentration of 0.4 g / dl (30 ° C.) ηo: Viscosity of dimethylformamide alone c: 0.4 Further, the thermoplastic resin to be mixed may be a mixture of these.

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

The former boron compound of the formula (I) can be produced, for example, by the following method (a) or (b).

(A) Method: General formula II [Wherein, 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 one terminal ether residue and having a total of 100 or less carbon atoms, and Y is (Where R is a hydrocarbon group having 1 to 82 carbon atoms, preferably 6 to 82 carbon atoms) or (Where R 'is a hydrocarbon group having 2 to 13, preferably 6 to 13 carbon atoms), and a, b and c are each 0 or 1. ｝], And one or more of the compounds represented by formula (1) are combined with 1 mol of boric acid or a boric acid triester of a lower alcohol having 4 or less carbon atoms.
The esterification reaction is carried out by reacting 0.5 mol of boric anhydride.

Method (b): Di (glycerin) borate or one or two of diols having a total carbon number of 206 or less, preferably 10 to 100, including a di (glycerin) borate residue in the middle.
Perform a polyetherification reaction on the species or more, or
One or more of them may be used in a total of 1 mole,
A dicarboxylic acid having 3 to 84 carbon atoms, preferably 8 to 84 carbon atoms (hereinafter referred to as a predetermined dicarboxylic acid) or 4 carbon atoms.
One of the following esters of a lower alcohol and a predetermined dicarboxylic acid or a halide of the predetermined dicarboxylic acid or a diisocyanate having 4 to 15, preferably 8 to 15 carbon atoms (hereinafter referred to as a predetermined diisocyanate). The species or two or more species are reacted in a total of 1 mol.

One or two or more semipolar organoboron polymer compounds (hereinafter, referred to as a predetermined semipolar organoboron polymer compound) thus produced, and a total of 5 to 5 carbon atoms having at least one hydroxyl group. 82, preferably 5
And 30 or more tertiary amines (hereinafter, referred to as a predetermined tertiary amine) in a proportion designed to be one boron atom to one basic nitrogen atom, Charged in a closed or open type reactor, under voltage, 20-200
C., preferably at 50-150 ° C.,
The antistatic agent of the present invention (hereinafter, referred to as a predetermined polymer charge transfer conjugate) is produced. At that time, when a polar solvent such as an alcohol, an ether or a ketone is allowed to coexist, the reaction can be performed more easily.

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

First, as a compound represented by the general formula II, which is a raw material of the method (a) for deriving a predetermined semipolar organic boron polymer compound, for example, diglycerin, di (glycerin) malonate, di (glycerin) maleate, (Glycerin) adipate, di (glycerin) terephthalate, di (glycerin) dodecanate, poly (9 mol) oxyethylene di (glycerin ether), di (glycerin) tolylene dicarbamate, di (glycerin) methylenebis (4,
Phenylcarbamate) and the like. On the other hand, as the predetermined dicarboxylic acid in the method (b), for example, malonic acid, maleic acid, succinic acid, adipic acid,
Sebacic acid, phthalic acid, terephthalic acid, dodecane diacid, dimer acid derived from linoleic acid, dodecyl maleic acid, dodecenyl maleic acid, octadecyl maleic acid, octadecenyl maleic acid, with an average degree of polymerization of 20 Maleic acid linking polybutenyl groups, and the like,
Examples of the predetermined diisocyanate include ethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, and methylene bis (4
-Phenyl isocyanate) and the like.

Next, as the predetermined tertiary amine to be reacted with a predetermined semipolar organic boron polymer compound, for example, diethylhydroxymethylamine, dimethyl 2-hydroxypropylamine, methyldi (2-hydroxyethylamine, tri (2-hydroxyethylamine) ) Amine, hydroxymethyldi (2-hydroxyethyl) amine, dibenzyl2-hydroxypropylamine, cyclohexyldi (2-hydroxyethyl) amine, ethylene oxide (1 to 25 mol) adduct of di (hexadecyl) amine, and monobutylamine Adducts of propylene oxide (1 to 26 mol).

In addition, in connection with the present invention, the type of amine material to be reacted with a predetermined semipolar organoboron polymer compound other than a predetermined tertiary amine, that is, a primary or secondary amine is a charge transfer conjugate. Cannot be produced successfully, and the resulting product is also an unstable compound, so that it is difficult to develop and maintain conductivity, and therefore, it is impossible to impart permanent antistatic properties to vinylidene fluoride resin.

In addition, when a tertiary amine having no hydroxysyl group is used, it is not possible to connect the generated polymer charge-transfer conjugates by multiple hydrogen bonds, so that the mobility of each chain is reduced. Since the size is increased, the state of aggregation in the base material is changed, and the charge leakage is insufficient.

The amount of the predetermined polymer charge-transfer conjugate of the present invention composition to the vinylidene fluoride resin varies depending on the purpose.
Generally, 0.01 parts by weight per 100 parts by weight of vinylidene fluoride resin
To 10 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, the high-performance antistatic property 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 occur, which is not preferable.

In the present invention, a residual amount of another thermoplastic resin may be mixed with the majority of the resin composition of the present invention. The type of the thermoplastic resin that can be mixed is not limited as long as the effect of the present invention is not impaired.
As thermoplastic resins that can be mixed, acrylic resins, polyolefins, polyvinyl chloride, polyvinylidene chloride,
Polyamide, polyester, polyvinyl fluoride, styrene resin, polyphenylene oxide and the like are preferably used.

Further, in the resin composition of the present invention, if necessary, a polymer material such as an inorganic filler, an organic filler, or an elastomer is blended in a range not significantly impairing the effects of the present invention to improve processability, rigidity, flexibility, and the like. You can also.

In addition, as a matter of course, other compounding agents such as stabilizers, antioxidants, lubricants, processing aids such as antiblocking agents, flame retardants, various pigments, dyes, and ultraviolet absorbers are appropriately used in addition to the above components. It is possible.

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

For example, as a kneading method, an open roll, an intensive mixer, a co-kneader, a single screw or twin screw extruder or the like is used.

As a specific example, a predetermined polymer charge transfer type conjugate and a desired additional component are mixed with the powdery or pelletized vinylidene fluoride resin of the present invention, and mixed with a Henschel mixer or the like. And melt-mixed in an extruder to form a pellet composition. The compounding components may be added to the resin during kneading, or may be added by a master batch method.

The obtained pellets are subjected to various moldings such as injection molding, extrusion molding, hollow molding, pressure molding, film molding, hot-press molding, spinning, and the like, and further subjected to secondary processing as necessary to obtain a molded product.

In the case of extrusion molding or hollow molding of a film or sheet, the resin composition of the present invention can be used in a single-sided surface layer or in a double-sided surface layer depending on the purpose, and can be multi-layered with another resin. Further, the resin composition layer of the present invention can be used by forming a resin composition layer on the surface of a molded product composed of a metal, a metal oxide or a resin containing a carbon-based conductive filler.

These molded articles are used in many fields for the purpose of preventing static electricity and removing static electricity. For example, in the case of antistatic, IC
It is applied to packaging materials for transportation and storage (carriers, trays, bags, racks, containers, etc.), parts boxes for electronic components, magnetic tapes, audio tape cases, slip sheets, and packaging materials for dangerous materials such as explosives. In addition, it is applied to static elimination rolls and sheets for removing static electricity, or to information recording paper and various resistors as semiconductor materials.

Further, when the resin composition of the present invention is formed into a film,
Since it has good water wettability, it is also suitable as building materials for civil engineering materials, agricultural house materials, and frozen food packaging materials.

Incidentally, for the resin composition of the present invention, silver, copper, brass,
A powdered or fibrous material such as iron, or a molded product in which a conductive filler such as carbon black or tin-coated titanium oxide or tin-coated silica coexists is a more accurate electromagnetic wave shielding material.

(Examples, etc.)

Examples will be described below in more detail. "Parts" described in these examples means parts by weight, and "%" means% by weight.

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

Example 1 To 100 parts of powder of a homopolymer of vinylidene fluoride (specific gravity: 1.77, apparent solvent viscosity of 9,000 poise), an appropriate amount of each of the predetermined polymer charge transfer type conjugates of the present invention was added, and a single screw extruder was used. At 220 ° C. to obtain pellets. A sheet was formed at 230 ° C. using the pellets to obtain a sheet having a thickness of 200 μm. After that, the sheet is
The sample was allowed to stand for 3 days and 30 days at constant temperature and humidity of 50 ° C and 50% RH.
After applying a voltage of KV and forcibly charging, remove
It is calculated by examining the presence or absence of residual charge after one minute. ) Was measured. In addition, as a comparative substance, known antistatic agents N, N
-Di (2-hydroxyethyl) stearylamine was selected and subjected to a similar test.

Here, a specific method for producing the predetermined polymer charge transfer conjugate used in the present example, for example, for the predetermined polymer charge transfer conjugates (1) and (2) will be described. It is on the street.

That is, the predetermined polymer charge-transfer type conjugate (1)
In a four-necked flask equipped with a stirring rod, a thermometer, an N ₂ gas inlet tube and a test tube, 1 mol of di (glycerin) borate and 1 mol of adipic acid are charged, and at 220 to 230 ° C. under the flow of N ₂ gas. It takes 4 hours to react until 2 moles of dehydration is obtained,
After confirming the increase in melt viscosity, the mixture is cooled to 70 ° C. Then, about the same amount of methyl ethyl ketone as the product was injected, and when a uniform solution was obtained, 1 mol of poly (25 mol) oxyethylene-dihexadecylamine was added, and the mixture was reacted at 70 to 75 ° C. for 1 hour. And under a reduced pressure of 150 mmHg, 1
It is obtained by distilling methyl ethyl ketone as a diluting solvent out of the system at 20 to 130 ° C. for 2 hours.

The predetermined polymer charge-transfer conjugate (5) is poly (9 mol) oxyethylene-di (glycerin ether)
1 mol and 1 mol of boric acid were charged and reacted at 150-230 ° C. under a stream of N _{2 for} 5 hours until dehydration for 3 mol was obtained. Let cool. Thereafter, about the same amount of isopropyl alcohol as the product was injected, and when a homogeneous solution was obtained, 1 mol of behenyl-di (2-hydroxyphenethyl) amine was added, and the mixture was reacted at 75 to 80 ° C. for 1 hour. , Under normal pressure, 15
It is obtained by distilling isopropyl alcohol as a diluting solvent out of the system at 0 to 160 ° C. for 3 hours. The method for producing the other predetermined polymer charge transfer conjugate is substantially the same as the above-described method.

The test results are as shown in Table 2. The vinylidene fluoride resin sheet of the present invention, in which the predetermined polymer charge-transfer conjugate was homogeneously dispersed, had no band even though the surface resistance was relatively large. It was found that there was almost no phenomenon that no charge was left and the performance deteriorated with time.

The apparent solvent viscosity of the vinylidene fluoride resin used in this example was measured using a capillary rheometer manufactured by Moncite Co., Ltd., with an orifice diameter of 0.041φ and L / D = 15 at 230 ° C. for 100 sec ^{− This} is the value obtained in ¹ .

Example 2 100 parts of a powder of vinylidene fluoride and propylene hexafluoride copolymer (specific gravity: 1.78, apparent solvent viscosity: 25,000 poise), a predetermined polymer charge transfer type conjugate of the present invention, an antiblocking agent and a slip agent Was added in an appropriate amount, and the mixture was melt-kneaded at 230 ° C. using a single screw extruder to obtain pellets. Using the pellets, a film was formed at 230 ° C. using a T-die extruder to obtain a film having a thickness of 50 μm. The electrical properties of these films were measured in the same manner as in Example 1.

The test results are as shown in Table 3, but the film of the composition of the present invention does not leave any charge, and there is hardly any economical decrease in performance. Also,
No problem such as deterioration of the film forming processability of the copolymer due to the addition of the predetermined polymer charge transfer type conjugate of the present invention was found at all.

Example 3 75% of vinylidene fluoride resin of Example 1 and acrylic resin
An appropriate amount of 25% of the predetermined polymer charge-transfer conjugate of the present invention was added, and the mixture was melt-kneaded at 220 ° C. with a twin-screw extruder to obtain pellets. Using the pellets, cylinder temperature with an injection molding machine
A sheet of 2 mmt × 100 mm × 100 mm was formed at 240 ° C. and a mold temperature of 60 ° C. The electrical properties of the sheet were measured in the same manner as in Example 1.

The test results are as shown in Table 4. The sheet made of the composition of the present invention did not leave any charge, and no deterioration in performance over time was observed.

A known antistatic agent, N, N-di (2-hydroxyethyl) stearylamine, was used as a comparative substance. In this case, bleeding out to the surface of the molded sheet was remarkable, and there was a problem in practical use. It was grasped.

Claims (1)

(57) [Claims] An antistatic resin composition comprising the following components (1) and (2). Component (1): Vinylidene fluoride resin Component (2): One or more semipolar organoboron polymer compounds represented by the following general formula I, and a total carbon number of 5 having at least one hydroxyl group A polymer charge transfer conjugate which is a reaction product of one or more tertiary amines of Nos. To 82 with a ratio of one boron atom to one basic nitrogen atom. [Wherein, 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 one terminal ether residue and having a total of 100 or less carbon atoms, and Y is (Where R is a hydrocarbon group having 1 to 82 carbon atoms) or (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 to 1000. ]