JP2000129135A - Antistatic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic resin composition having excellent durability of antistatic effect, capable of developing excellent water resistance and mechanical strengths by mixing a hydrophilic polymer having a specific water absorption ratio with a specified hydrophobic thermoplastic resin in a prescribed weight ratio. SOLUTION: This composition comprises (A) a hydrophilic polymer (preferably polyether ester amide, etc.), having 10-100% water absorption ratio measured by ASTM-D 570 method and (B) a hydrophobic thermoplastic resin (preferably polyacrylic resin, polystyrene-based resin, etc.), having <=0.8 difference in solubility parameter between the component A and the component B in the weight ratio of the component A:B of 2-40:60-98. A polyether ester amide derived from a polyamide containing carboxy groups at both ends, having 200-5,000 number-average molecular weight and a polyoxyalkylene ether of bisphenol and/or a polyalkylene glycol, having 300-5,000 number-average molecular weight is preferable as the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an antistatic resin composition. More specifically, the present invention relates to an antistatic resin composition which has excellent durability of an antistatic effect, and has good water resistance and mechanical strength.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting an antistatic property to a thermoplastic resin having a high insulating property, a method of kneading a low molecular weight surfactant; a method of kneading a metal filler or conductive carbon black; However, since the resin composition obtained by the method of the present invention is effective due to bleed out of a low molecular weight surfactant, in addition to losing the antistatic effect by wiping with water, there is a problem that surface roughness occurs, Although the resin composition obtained by the above method has excellent durability of the antistatic effect, it requires a large amount of a metal filler or the like to be added, so that there is a problem that the impact resistance is reduced.
Therefore, as a method for solving these problems, a method of kneading a water-insoluble hydrophilic polymer has been proposed.

[0003]

However, when a hydrophilic polymer having a high water absorption is used, in applications where water resistance is required, water absorption causes surface roughness, surface blistering, or peeling. Had disadvantages. Further, when a hydrophilic polymer having a large difference in solubility parameter from the thermoplastic resin to be kneaded is used, there is a problem that the compatibility is deteriorated and the mechanical strength of the resin is reduced. An object of the present invention is to provide an antistatic resin composition having excellent durability of an antistatic effect, good water resistance and good mechanical strength.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention. That is, the present invention provides a hydrophilic polymer (A) having a water absorption of 10 to 100% as measured by the ASTM-D570 method,
A hydrophobic thermoplastic resin (B) having a solubility parameter difference of 0.8 or less from (A), and (A):
The weight ratio of (B) is (2 to 40): (60 to 98), which is an antistatic resin composition.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The hydrophilic polymer (A) used in the present invention includes polyetheresteramide, polyetheramideimide, epihalohydrin / alkylene oxide copolymer, acrylamide copolymer, ethylene / unsaturated acid Salt or ethylene / (meth) acrylate / unsaturated acid salt copolymer, polyether ester, methoxypolyethylene glycol (meth) acrylate copolymer, polyether group-containing ethylene / vinyl acetate copolymer (ethylene / vinyl alcohol copolymer) And a mixture of two or more thereof. Of these, polyetheresteramides,
Polyether amide imide, alkylene oxide / epihalohydrin copolymer, acrylamide copolymer, ethylene / unsaturated acid salt or ethylene / (meth) acrylate / unsaturated acid salt copolymer and polyether ester are preferable, and polyether is particularly preferable. Ester amides are preferred because they can exhibit excellent antistatic properties at low water absorption.

The water absorption measured by the ASTM-D570 method (A) is usually 10 to 100%, preferably 40 to 9%.
0%, particularly preferably 60-80%. Water absorption rate is 1
If it exceeds 00%, swelling causes surface roughness and surface blistering, and if it is less than 10%, the antistatic properties are poor. The water absorption can be measured by the method described in ASTM-D570 (at 23 ° C., after 24 hours). The solubility parameter (SP value) of (A) is usually 8.5 to 14, preferably 9 to 1.
2. The SP value is calculated, for example, by the method of Fedors (P
oligomerEngineer Science, vo
l. 14, p. 152).

Of the above (A), those particularly preferred as polyetheresteramides are described, for example, in
No. 287547, a polyamide (a1) having carboxyl groups at both terminals and having a number average molecular weight of 200 to 5,000, a polyoxyalkylene ether (a2) of bisphenols having a number average molecular weight of 300 to 5,000 and / or Or a polyetheresteramide derived from polyalkylene glycol (a3). The above (a2) is used alone as the polyether component or (a2)
By using in combination with 3), a polyetheresteramide whose water absorption is controlled to 60 to 80% can be obtained.

The above (a1) includes (1) a compound having 6 to 6 carbon atoms.
A lactam ring-opened polymer of 12 or more; (2) a polycondensate of an aminocarboxylic acid having 6 to 12 or more carbon atoms; or (3) a dicarboxylic acid having 4 to 20 carbon atoms and 4 to 12 carbon atoms. Alternatively, a polycondensate with a diamine or more is used. Examples of the lactam (1) include caprolactam, enantholactam, laurolactam, undecanolactam and the like. Examples of the aminocarboxylic acid (2) include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecane Acids and the like. Examples of the dicarboxylic acid (3) include adipic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, and isophthalic acid. Examples of the diamine include hexamethylene diamine, heptamethylene diamine, and octamethylene diamine. , Decamethylenediamine and the like. Two or more of the above-mentioned amide-forming monomers can be used in combination. Among these, preferred are caprolactam, 12-aminododecanoic acid and adipic acid-hexamethylenediamine, and particularly preferred is caprolactam.

(A1) is obtained, for example, by using a dicarboxylic acid having 4 to 20 carbon atoms as a molecular weight modifier and subjecting the amide-forming monomer to ring-opening polymerization or polycondensation in a conventional manner in the presence of the dicarboxylic acid. Can be The carbon number 4 or more
As the dicarboxylic acid of 20, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Aliphatic dicarboxylic acids such as sebacic acid, undecandioic acid and dodecandioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid;
Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-dicarboxylic acid; 3
Alkali metal salts of 3-sulfoisophthalic acid such as sodium sulfoisophthalate and potassium 3-sulfoisophthalate; and mixtures of two or more thereof. Among these, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and particularly preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate. It is.

The number average molecular weight of (a1) is usually from 200 to
It is 5,000, preferably 500-3,000. When the number average molecular weight is less than 200, the heat resistance of the polyetheresteramide itself decreases, and when the number average molecular weight exceeds 5,000, the reactivity decreases, so that much time is required for producing the polyetheresteramide.

The polyoxyalkylene ether (a2) of a bisphenol is a bisphenol having 2 to 4 carbon atoms.
By adding an alkylene oxide of the formula
As the bisphenols, bisphenol A (4,
4'-dihydroxydiphenyl-2,2-propane),
Bisphenol F (4,4'-dihydroxydiphenylmethane), bisphenol S (4,4'-dihydroxydiphenylsulfone), 4,4'-dihydroxydiphenyl-2,2-butane and the like are preferred, and bisphenol is preferred. A. 2 to 4 carbon atoms
Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2- or 1,4-butylene oxide, and a mixture of two or more thereof. Of these, particularly preferred is ethylene oxide.

The number average molecular weight of (a2) is usually 300
5,000, preferably 1,000-3,000, more preferably 1600-3,000. When the number average molecular weight is less than 300, the water absorption of the polyetheresteramide itself decreases, so that the antistatic property becomes insufficient,
If it exceeds 5,000, the reactivity decreases, so that a great amount of time is required for producing the polyetheresteramide.

Examples of the polyalkylene glycol (a3) include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyhexamethylene glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. Among them, preferred is polyethylene glycol.

The number average molecular weight of (a3) is usually 300
5,000, preferably 1,000-3,000, more preferably 1600-3,000. When the number average molecular weight is less than 300, the water absorption of the polyetheresteramide itself decreases, so that the antistatic property becomes insufficient,
If it exceeds 5,000, the reactivity decreases, so that a great amount of time is required for producing the polyetheresteramide.

(A2) and / or (a3) constituting the polyetheresteramide is usually in the range of 20 to 80% by weight based on the total weight of (a1) and (a2) and / or (a3). Used in If the amount is less than 20% by weight, the water absorption of the polyetheresteramide itself is reduced, so that the antistatic property is poor. If the amount is more than 80% by weight, the water absorption exceeds 100%, so that the water resistance of the resin composition is reduced. Further, the ratio of (a2) / (a3) can be changed over a wide range, but the weight ratio is 100/0 to 5/95, particularly 10/0.
0/0 to 50/50 are preferred.

Examples of the method for producing the polyetheresteramide include, but are not particularly limited to, the following methods and methods. Production method: A method in which (a1) is formed by reacting an amide-forming monomer and a dicarboxylic acid, and (a2) and / or (a3) are added thereto, and a polymerization reaction is performed at high temperature and reduced pressure. Production method: An amide-forming monomer and a dicarboxylic acid and (a2) and / or (a3) are simultaneously charged into a reaction vessel, and subjected to a pressure reaction at a high temperature in the presence or absence of water as an intermediate (a1). And then (a1) and (a2) and / or (a3) under reduced pressure
To carry out a polymerization reaction with

In the above-mentioned polymerization reaction, a known esterification catalyst is usually used. Examples of the catalyst include antimony catalysts such as antimony trioxide; tin catalysts such as monobutyltin oxide; titanium catalysts such as tetrabutyl titanate; zirconium catalysts such as tetrabutyl zirconate and zirconyl acetate; acetic acid such as zinc acetate. Metal salt catalysts and the like can be mentioned. These usages are
It is usually 0.1 to 5 parts by weight based on the total weight of (a1), (a2) and / or (a3).

The reduced viscosity of the polyetheresteramide (ηSP / C, C = 0.5 wt% m-cresol solution, 2
(5 ° C.) is not particularly limited, but is usually 0.5 to 4, preferably 0.6 to 3. If the reduced viscosity is less than 0.5, the heat resistance of the polyetheresteramide itself is poor, and if it exceeds 4, the moldability of the resin composition is reduced.

Among the above (A), particularly preferred as the polyether amide imide are, for example, JP-B-7-1
No. 19342, (a) caprolactam,
(B) a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring and (c) polyoxyethylene glycol or at least 50% by weight of polyoxyethylene glycol and a polyoxyethylene glycol other than polyoxyethylene glycol. Derived from a mixture of oxyalkylene glycols, wherein the content of glycol component (c) is 8
A polyether amide imide having a reduced viscosity at 5 to 30% by weight and a temperature of 30 ° C. of 1.5 or more.

As the component (b), a trivalent or tetravalent aromatic carboxylic acid capable of reacting with an amino group to form at least one imide ring or an anhydride of these carboxylic acids is used. Examples of the trivalent carboxylic acid include 1,2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, 2,6,7-naphthalenetricarboxylic acid, and 3,3 ′, 4-diphenyltricarboxylic acid Benzophenone-3,3 ', 4-tricarboxylic acid, diphenylsulfone-3,3', 4-tricarboxylic acid, diphenylether-3,3 ', 4-tricarboxylic acid and the like. Examples of the tetravalent carboxylic acid include pyromellitic acid, diphenyl-2,2 ′, 3,3′-tetracarboxylic acid, and benzophenone-2,2 ′, 3,3′-.
Tetracarboxylic acid, diphenylsulfone-2,2 ',
3,3'-tetracarboxylic acid, diphenyl ether-
2,2 ′, 3,3′-tetracarboxylic acid and the like can be mentioned. These carboxylic acids correspond to the glycol component 1 of (c).
It is usually used in the range of 0.9 to 1.1 mol (substantially equimolar) with respect to the mol.

As the component (c), polyoxyethylene glycol or a mixture of polyoxyethylene glycol and a polyoxyalkylene glycol other than polyoxyethylene glycol is used.

The number average molecular weight of the polyoxyethylene glycol used is not particularly limited, but is preferably 500 to 5,000.
It is preferred that When the number average molecular weight is less than 500, the water absorption of the polyether amide imide itself is reduced, so that the antistatic property becomes insufficient. When the number average molecular weight exceeds 5,000, much time is required for producing the polyether amide imide.

As the polyoxyalkylene glycol which can be used in combination with the polyoxyethylene glycol, polyoxytetramethylene glycol having a number average molecular weight of 500 to 5,000, modified polyoxytetramethylene glycol, polyoxypropylene glycol and the like are used. be able to. As the modified polyoxytetramethylene glycol, the conventional polyoxytetramethylene glycols - include those obtained by replacing the (CH _{2) 4} part of -O- with -R-O-. Here, R has 2 to 10 carbon atoms.
Alkylene group, specifically, ethylene group, 1,
2-propylene group, 1,3-propylene group, 2-methyl-1,3-propylene group, 2,2-dimethyl-1,3-
Preferable examples include a propylene group, a pentamethylene group, and a hexamethylene group. The amount of modification is not particularly limited, but is usually selected in the range of 3 to 50% by weight.

The content of the polyamide imide constituting the polyether amide imide is usually 15 to 70% by weight. Fifteen
If the amount is less than 100% by weight, the water absorption of the polyetheramideimide itself exceeds 100%, so that the water resistance of the resin composition decreases. If the amount exceeds 70% by weight, the antistatic property is poor. The number average molecular weight of the polyamideimide is preferably from 500 to 3,000, and more preferably from 500 to 2,000. If the number average molecular weight of the polyamide imide is less than 500, the heat resistance of the polyether amide imide itself decreases,
If it exceeds 3,000, the mechanical strength of the resin composition decreases.

The method for producing the polyether amide imide includes the following methods, but is not particularly limited. Caprolactam component (a), aromatic polycarboxylic acid component (b) and glycol component (c)
The components (b) and (c) are mixed in such a ratio that they become substantially equimolar, and the resulting polymer has a water content of 0.1 to 1% by weight.
150-300 ° C., more preferably 18
This is a method of polymerizing at 0 to 280 ° C. In the present method, the reaction temperature can be raised stepwise during the dehydration condensation. At this time, some caprolactam remains unreacted, but is removed from the reaction mixture by distillation under reduced pressure. The reaction mixture after removing the unreacted caprolactam may be subjected to reduced pressure at 200 to 300 ° C.,
Higher polymerization can be achieved by post-polymerization at 30 to 280 ° C.

The reduced viscosity of the polyether amide imide (0.5% by weight m-cresol solution, 30 ° C.) is not particularly limited, but is preferably 1.5 or more. If the reduced viscosity is less than 1.5, the moldability of the resin composition will decrease.

The epihalohydrin / alkylene oxide copolymer includes, for example, an epihalohydrin / alkylene oxide copolymer described in JP-B-7-84564. Examples of the epihalohydrin monomer include epichlorohydrin, epibromohydrin,
Includes epiiodohydrin and epifluorohydrin, with epichlorohydrin being particularly preferred. Examples of the epihalohydrin / alkylene oxide copolymer include epihalohydrin, one or more selected from 1,2-epoxide monomers (particularly alkyl glycidyl ethers) and alkylene oxides having 2 to 4 carbon atoms (particularly ethylene oxide and / or propylene oxide). Copolymers with two or more comonomers are included. Preferred copolymers have a weight ratio of epihalohydrin to comonomer of (5-95) :( 95-5), preferably (10-95).
60): (90 to 40), particularly preferably a copolymer comprising epichlorohydrin and ethylene oxide and having a weight ratio of about 50:50.

The epihalohydrin / alkylene oxide copolymer is easily prepared by bulk or solution polymerization using a known catalyst such as water and optionally a small amount of a chelating agent and a catalyst formed by the reaction of an organoaluminum compound. it can. The number average molecular weight of the copolymer is usually 30,000 to 100,000 or more,
Preferably it is 60,000-90,000.

The acrylamide-based copolymer in the above (A) includes, for example, 65 to 99 mol% of ethylene units represented by-[CH ₂ -CH ₂ ]-described in JP-A-4-198308; General formula (Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms), and 0 to 15 mol% of an acrylate unit represented by the following general formula: Wherein R ² is an alkylene group having 2 to 8 carbon atoms, R ³ and R ⁴ are alkyl groups having 1 to 4 carbon atoms, and R ⁵ is an alkyl group, arylalkyl group or A ring alkyl group, X is a halogen atom, CH ₃ OSO ₃ or C
Represents ₂ H ₅ OSO ₃ . And acrylamide units comprising 1 to 35 mol% of acrylamide units represented by the formula (1).

The content of the ethylene unit is particularly preferably 85 to 97 mol% from the viewpoint of the balance between the antistatic property and the moldability. The content of the acrylate unit represented by the general formula (1) is preferably from 1 to 15 mol%, particularly preferably from 3 to 7 mol%, from the viewpoint of the balance between antistatic properties and mechanical properties. Specific examples of R ¹ in the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Examples thereof include an n-butyl group and an isobutyl group, and a methyl group and an ethyl group are particularly preferable from the viewpoint of maintaining the moldability of the acrylamide copolymer. The content of the acrylamide unit represented by the general formula (2) is particularly preferably 3 to 15 mol% from the viewpoint of the balance between antistatic properties and water resistance. In the general formula (2), specific examples of R ² include an ethylene group, a propylene group, a hexamethylene group, a neopentylene group and the like, and an ethylene group and a propylene group are preferable in view of easiness of production and economy, Particularly, a propylene group is preferred. Specific examples of R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group and the like, and a methyl group and an ethyl group are preferred from the viewpoint of imparting antistatic properties. Specific examples of R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
alkyl groups such as sec-butyl group, n-octyl group and n-lauryl group; arylalkyl groups such as benzyl group; alicyclic alkyl groups such as cyclohexyl group and methylcyclohexyl group; and the heat resistance of acrylamide copolymers. From the viewpoint of properties, a linear alkyl group and an arylalkyl group are preferred, and a lower alkyl group is preferred from the viewpoint of imparting antistatic properties. Particularly preferred R ⁵ is methyl and ethyl. Specific examples of X are Cl, Br, a halogen atom, such as I; include CH ₃ 0SO ₃ and C ₂ H ₅ OSO _3, Cl terms of antistatic property-imparting property, CH ₃ 0S
O ₃ and C ₂ H ₅ OSO ₃ are particularly preferred.

The weight average molecular weight of the acrylamide copolymer is preferably from 1,000 to 50,000, and particularly preferably from 3,000 to 35,000 from the viewpoint of the balance between heat resistance and moldability. As a method for producing such an acrylamide-based copolymer, for example, a monomer mixture of a corresponding ratio is randomly copolymerized by a known method, and the obtained copolymer is quaternized (an alkyl halide such as methyl chloride, dimethyl Cation modification with a dialkyl sulfate such as sulfuric acid).

The ethylene / unsaturated acid salt or ethylene / (meth) acrylate / unsaturated acid salt copolymer in the above (A) includes, for example, ethylene / unsaturated acid copolymer described in JP-A-8-269276. Or ethylene /
An ionomer in which a part or all of the carboxyl groups of the random copolymer of (meth) acrylate / unsaturated carboxylic acid is neutralized with an alkali metal is exemplified. Examples of the unsaturated carboxylic acid constituting the copolymer include (meth) acrylic acid; fumaric acid, (anhydride) maleic acid;
Examples thereof include a monoalkyl (C1-4) ester of the dibasic acid and a mixture of two or more of these. Particularly preferred is (meth) acrylic acid. Examples of the (meth) acrylate include alkyl (meth) acrylates (1-8 carbon atoms) such as methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include n-butyl acid and a mixture of two or more of these. Particularly preferred is ethyl (meth) methacrylate. Such a copolymer can be obtained by random copolymerization of each polymerization component at a high temperature and a high pressure by an ordinary method.

As the alkali metal for neutralizing the carboxyl group of the copolymer to obtain an ionomer, lithium, sodium, potassium, rubidium, cesium and the like are used, and potassium and sodium are particularly preferable.

As the ionomer, ethylene is 60
-95% by weight, especially 70-90% by weight, 5-40% by weight of unsaturated carboxylic acid or unsaturated carboxylate component,
Especially 10 to 30% by weight, (meth) acrylate is 0 to 3
Those having a ratio of 0% by weight, especially 5 to 20% by weight are preferred. Further, the MFR of the ionomer (190 ° C.,
2.16 kg) is preferably 1 to 20 from the viewpoint of moldability. Particularly preferred as the ionomer is a copolymer comprising units of ethylene / ethyl acrylate / acrylate (sodium salt) in a weight ratio of about 90/10/10.

From the viewpoint of antistatic properties, the content of alkali metal cations in the ionomer is desirably in the range of 0.4 to 4 mol, preferably 0.6 to 2 mol per 1 kg of the ionomer. Further, it is preferable to use those having a degree of neutralization of the carboxyl group in the ionomer (average degree of neutralization when two or more ionomers are used) of 60 mol% or more, particularly 70 mol% or more.

Examples of the polyetherester in the above (A) include polyetheresters described in Japanese Patent Publication No. 58-19696. The polyetherester is a polyester having a segment composed of polyetherglycol or copolyetherglycol. For example, one or more of the glycol components exemplified as the constituent materials of the polyetheresteramide or polyetheramideimide and a dicarboxylic acid (isophthalic acid) Polycondensation with one or more aromatic dicarboxylic acids such as acid and terephthalic acid; aliphatic dicarboxylic acids such as succinic acid, glutaric acid and adipic acid) or their ester-forming derivatives (lower alkyl esters, anhydrides, etc.) It can be obtained by a reaction or a transesterification reaction between the above glycol component and polyethylene terephthalate, polybutylene terephthalate, or the like. The polyether segment content of the polyetherester is preferably from 30 to 70% by weight, particularly from 40 to 60% by weight from the viewpoint of antistatic properties and moldability, and the melting point (thermal softening point) is usually 100 ° C or higher, preferably 120 ° C or higher. Those having a temperature of up to 210 ° C. are preferred.

As the hydrophobic thermoplastic resin (B) used in the present invention, polyolefin resins [for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin, etc.]; Polyacrylic resin [eg polymethyl methacrylate]; polystyrene resin [eg polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / Styrene copolymer (MBS resin), styrene /
Methyl methacrylate copolymer (MS resin), etc.]; polyester resins [eg, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polybutylene adipate,
Polyethylene adipate or the like]; polyamide resin [for example, nylon 66, nylon 69, nylon 612,
Nylon 6, Nylon 11, Nylon 12, Nylon 4
6, nylon 6/66, nylon 6/12, etc.]; polycarbonate resins [for example, polycarbonate, polycarbonate / ABS resin alloy, etc.]; polyacetal resins; thermoplastic polyurethane resins. The melt index of (B) (230C, 2.16k)
g) is usually 0.1 to 100. Among these, preferred are polyacrylic resin, polystyrene resin,
Polyacetal resins, polyester resins, polycarbonate resins, thermoplastic polyurethane resins, and polyamide resins are particularly preferable. Polystyrene resins, polyacetal resins, polyester resins, polycarbonate resins, and thermoplastic polyurethane resins are particularly preferable.

The difference in solubility parameter (SP value) between the hydrophilic polymer (A) and the above (B) must be 0.8 or less, preferably 0.5 or less. By setting the difference in SP value within the above range, the compatibility between (A) and (B) is improved,
It is possible to obtain a resin composition having a good balance between mechanical strength and antistatic properties.

The weight ratio (A) :( B) of (A) and (B) in the resin composition of the present invention is usually (2-40):
(60-98), preferably (5-30): (70-9)
5). When the ratio of (A) is less than 2, the antistatic property becomes insufficient, and when it exceeds 40, water resistance and mechanical strength are undesirably reduced.

The resin composition of the present invention can be obtained by melt-mixing (A) and (B). An ordinary method is used for melt mixing, and generally, pellet-like or powder-like polymers are mixed with an appropriate mixer, for example, a Henschel mixer, and then melt-mixed with an extruder and pelletized. It can be obtained by: As a molding method, an injection molding method is preferable.

A molded article comprising the resin composition of the present invention has excellent water resistance, permanent antistatic properties and mechanical strength, and also has good coating properties and printability. Examples of a method for coating the molded article include, but are not limited to, air spray, airless spray, electrostatic spray, dip coating, roller coating, and the like. Examples of the paint include a polyester melamine resin paint, an epoxy melamine resin paint, an acrylic melamine resin paint, and an acrylic urethane resin paint. The coating film pressure (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm. Also,
As a method for printing on the molded article, any printing method generally used for printing plastics can be used, and examples thereof include gravure printing, flexographic printing, screen printing, and offset printing.

To the resin composition of the present invention, other known resin additives can be optionally added as needed in accordance with the intended use, as long as the properties of the composition are not impaired.
Examples of the additives include pigments, dyes, fillers, nucleating agents, glass fibers, lubricants, plasticizers, release agents, antioxidants, flame retardants, ultraviolet absorbers, compatibilizers, and the like.

The resin composition of the present invention provides a molded article having water resistance,
Good mechanical strength, durability of antistatic effect, paintability,
Since it is also excellent in printability and the like, it is suitably used as a molding material for various applications requiring antistatic properties, for example, housing products such as home appliances / OA equipment, game machines, office equipment, various plastic containers, and automobile parts. .

[0044]

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples. In the following, parts and% indicate parts by weight and% by weight, respectively.

[Production Example of Hydrophilic Polymer (A)] Production Example 1 In a 3 L stainless steel autoclave, 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, 0.3 parts of “Irganox 1010” and water 6 After charging with nitrogen and purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours while sealing under pressure to obtain 96 parts of a polyamide oligomer of oxidized 112 having carboxyl groups at both ends. Next, 192 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 2,000 and 0.5 part of zirconyl acetate were added, and the mixture was added at 245 ° C. and 1 mmH
Polymerization was performed for 5 hours under a reduced pressure of not more than g to obtain a viscous polymer. The polymer was taken out in a strand form on a belt and pelletized to obtain a polyetheresteramide. Reduced viscosity of this product (ηSP / C, m-cresol solvent, 25 ° C., C = 0.5% by weight, and so on)
Was 2.10, the water absorption (after 24 hours at 23 ° C.) measured by the method described in ASTM-D570 was 72%, and the solubility parameter obtained by calculation was 9.9. This polyetheresteramide is abbreviated as [A-1] below.

[Production Example of Comparative Hydrophilic Polymer] Production Example 2 105 parts of ε-caprolactam, 17.1 parts of adipic acid, 0.3 parts of “Irganox 1010” and 6 parts of water were charged into a 3 L stainless steel autoclave. After purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours while sealing under pressure to obtain 117 parts of a polyamide oligomer having an acid value of 110 and having carboxyl groups at both ends. Then, 175 parts of polyoxyethylene glycol having a number average molecular weight of 1,500 and 0.5 parts of zirconyl acetate were added, and the mixture was polymerized at 245 ° C. under a reduced pressure of 1 mmHg or less for 5 hours to obtain a viscous polymer. Hereinafter, the same operation as in Production Example 1 was performed to obtain a polyetheresteramide. Its reduced viscosity is 2.30, AS
Water absorption measured by the method described in TM-D570 (23 ° C,
24 hours) was 120%, and the calculated solubility parameter was 9.6. This polyetheresteramide is abbreviated as [A-2] below.

Examples 1-2, Comparative Examples 1-4 The ratios (A) and (B) shown in Table 1 were blended in a Henschel mixer and then melt-kneaded in a vented twin-screw extruder. An antistatic resin composition of the invention and a comparative resin composition were obtained. Table 1 shows the water absorption of (A), the difference between the solubility parameters of (A) and (B), and the mixing ratio.

[0048]

[Table 1] (Note) [B-1]: Acrylic resin [trade name “Acrypet VH”, manufactured by Mitsubishi Rayon Co., Ltd., solubility parameter = 9.3] [B-2]: ABS resin [trade name “ABS10”, Techno Polymer B. Ltd., solubility parameter = 10.7] [B-3]: polypropylene [trade name "J609H", Grand Polymer Co., Ltd., solubility parameter = 8.0]

Example 3 Ethylene oxide / epichlorohydrin copolymer having a water absorption of 50% [trade name "Statite"; F. Goodrich Co.] 2 parts, [A-1] 8 parts and [B-2] 9
After blending 0 parts with a Henschel mixer, the mixture was melted and kneaded with a vented twin screw extruder to obtain an antistatic resin composition of the present invention.

Performance Tests Test pieces were prepared from the antistatic resin compositions of the present invention of Examples 1 to 3 and the resin compositions of Comparative Examples 1 to 4 using an injection molding machine, and the test methods described below were used. Various physical properties were measured. Table 2 shows the results. (1) Izod impact strength: based on ASTM D256. (2) Flexural modulus: according to ASTM D790. (3) Surface specific resistance: Injection molded piece was 23 ° C and humidity was 50
After conditioning for 48 hours or more in a% RH atmosphere, measurement was performed with a super insulation meter (manufactured by Toa Denpasha Co., Ltd.). (4) Water resistance: Evaluated by immersing the molded article in 50 ° C. hot water for 72 hours and observing the surface. Evaluation criteria ○: No change ×: Surface roughness (5) Water resistance after coating: A commercially available two-part curable acrylic urethane resin is electrostatically coated on the molded piece, baked at 80 ° C. for 2 hours, and then the molded product is treated with 50 parts. Immersed in warm water for 72 hours.
A Goban eye adhesion test was performed according to K5400. Evaluation criteria ○: No peeling ×: With peeling

[0051]

[Table 2]

As is clear from Table 2, the resin compositions of the present invention of Examples 1 to 3 were compared with the compositions of Comparative Examples 1 to 4,
Extremely good balance of water resistance, water resistance after coating, mechanical properties and antistatic properties.

[0053]

The resin composition of the present invention has an extremely good balance between water resistance, mechanical properties and permanent antistatic properties, and is excellent in coatability and printability. Due to the above effects, molded articles made of the antistatic resin composition of the present invention are useful especially as molding materials for home appliances / OA equipment, game equipment, housing products for office equipment, various plastic containers, automobile parts and the like. is there.

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Claims (6)

[Claims] 1. A hydrophilic polymer (A) having a water absorption of 10 to 100% as measured by the ASTM-D570 method,
A hydrophobic thermoplastic resin (B) having a solubility parameter difference of 0.8 or less from (A), and (A):
The weight ratio of (B) is (2 to 40): (60 to 98). 2. A method according to claim 1, wherein (A) is a polyetheresteramide,
At least one selected from polyether amide imide, epihalohydrin / alkylene oxide copolymer, acrylamide copolymer, ethylene / unsaturated acid salt or ethylene / (meth) acrylate / unsaturated acid salt copolymer, and polyether ester The resin composition according to claim 1, wherein the resin composition is a hydrophilic polymer. 3. The resin composition according to claim 1, wherein (A) is a polyetheresteramide. 4. A polyamide (a) having a carboxyl group at both terminals and having a number average molecular weight of 200 to 5,000.
A polyetheresteramide derived from 1) and a polyoxyalkylene ether (a2) and / or a polyalkylene glycol (a3) of a bisphenol having a number average molecular weight of 300 to 5,000.
The resin composition according to any one of the above. 5. The method according to claim 1, wherein (B) is at least one thermoplastic resin selected from a polyacrylic resin, a polystyrene resin, a polyacetal resin, a polyester resin, a polycarbonate resin, a polyurethane resin and a polyamide resin. 6. The resin composition according to any one of 1 to 5. 6. A molded article obtained by applying a coating or printing to a molded article comprising the resin composition according to claim 1.