KR0136244B1 - Acrylic resin composition - Google Patents

Abstract

It contains one or more polyamide elastomers, acrylic resins and optionally one or more electrolytes containing hard and soft segments in specific proportions, and has excellent permanent antistatic properties, good transparency, extremely low coloring, and inexpensiveness. The acrylic resin composition which has very little fall of transparency even when immersed in water.

Description

Acrylic countdown composition

Acrylic resins have been widely used as materials for various parts of, for example, electrical appliances, home appliances, and OA devices because of their excellent transparency and rigidity.

However, since acrylic resin has a high surface resistivity and can be easily charged by friction, etc., for example, garbage or dust is adhered, the appearance of the acrylic resin becomes poor or an undesirable situation is caused by electrostatic charging in parts such as electronic devices. It is disadvantageous. Therefore, it is desired to develop a material having antistatic properties as well as excellent properties of acrylic resins.

As a method of providing antistatic property to acrylic resin, the method of kneading surfactant to acrylic resin or applying surfactant to the surface of acrylic resin is well known, for example. However, according to the method, since the surfactant present on the surface is easily removed by water washing, friction, etc., it is difficult to permanently give an antistatic property.

As a method for imparting permanent antistatic properties, for example, (1) a method of kneading a vinyl copolymer having a polyoxyethylene chain structure and a sulfonate, carboxylate or quaternary ammonium salt structure with an acrylic resin ( Japanese Patent Application Laid-Open Nos. 55-36237 and 63739), (2) a polyether ester amide, for example, methyl tetramethyl-butadiene-styrene copolymer (MBS resin) or methyl methacrylate-acrylonitrile-butadiene- Method of kneading in styrene copolymer (MABS resin) (Japanese Patent Laid-Open No. 62-119256), and (3) modified vinyl having at least one functional group such as polyamide elastomer, carboxyl group, ethoxy group or hydroxyl group A system polymer and optionally a rubber graft copolymer are added to an acrylic resin to obtain a permanent antistatic resin having no surface peeling and excellent surface gloss. This allowed -308444 disclose a first call) are disclosed. Further, for example, a method of kneading (4) polyether block amide to an acrylic resin is also disclosed (Japanese Patent Laid-Open No. 64-90246).

However, in the method described in (1) above, the blended vinyl copolymer is a special vinyl monomer and therefore expensive, and the manufacturing cost of the acrylic resin composition obtained by blending the vinyl copolymer inevitably rises. In particular, the method disclosed in Japanese Patent Laid-Open Nos. 55-36237 is disadvantageous in that the intrinsic heat resistance of acrylic resin is lowered, for example, because the amount of the vinyl copolymer blended is large. On the other hand, in the method described in (2), the transparency of the resulting composition is maintained by adjusting the refractive index difference between the amorphous polyether ester amide and the MBS resin or the MABS resin to 0.02 or less, and as a result, the degree of freedom of the blend is low. In addition, this method is disadvantageous in that when using poly (methyl methacrylate), which is a typical acrylic resin, it is difficult to adjust the refractive index difference to a value within a desired range and transparency tends to be lowered.

The antistatic resin according to the above (3) adds a modified vinyl polymer having at least one special functional group to a composition of a substantially incompatible arc-based resin and a polyamide elastomer to improve affinity, thereby preventing delamination. Obtained by imparting antistatic effect. However, the antistatic resin is not always satisfactory in transparency. In addition, transparency of antistatic resin as described in said (4) is not satisfactory practically when judged by the value of total light transmittance.

Acrylic resins are remarkably characterized by excellent transparency, but when the other high molecular weight compounds are kneaded with acrylic resins to impart permanent antistatic properties to the acrylic resins, the affinity between the acrylic resins and the other high molecular weight compounds is poor. The transparency is often lowered. Even if a product having good transparency can be obtained, a sufficient antistatic effect cannot be obtained or the heat resistance is lowered. In addition, when producing and using a high molecular weight compound having a complex structure in order to exhibit a sufficient antistatic effect, it is possible to obtain an acrylic resin having a high production cost, rich in versatility, inexpensive, and practically satisfactory antistatic properties. Can not.

Under such circumstances, development of an acrylic resin composition having excellent permanent antistatic properties, inexpensiveness, and good transparency has been desired.

The inventors of the present invention have studied acrylic resin compositions having excellent antistatic properties and transparency, and polyamide-imide elastomers having a low content of hard segments have good affinity with acrylic resins and are finely dispersed in acrylic resins to have excellent antistatic properties. It was first discovered that a clear composition was obtained. We have disclosed this finding in Japanese Patent Laid-Open No. 2-255753. However, the polyamide-imide elastomer is pale yellow, which is not always satisfactory because the acrylic resin containing the polyamide-imide elastomer is colored pale yellow. In addition, the polyamide-imide elastomer is not always satisfactory because transparency is lowered when the acrylic resin composition is immersed in water.

Disclosure of the Invention

In the above situation, the present invention has been completed to provide an acrylic resin composition having excellent permanent antistatic properties, good transparency, very faint coloring, and very low deterioration of transparency even when water is immersed.

The present inventors made extensive studies to develop an acrylic resin composition having the above-described desirable properties. The following findings were found: A soft segment composed of a polyether segment containing a specific ratio of polyoxyethylene residues and having a specific number average molecular weight. And polyamide elastomers obtained by block polymerization of hard segments containing polyamide segments in a specific ratio have little coloration and good affinity with acrylic resins: by blending polyamide elastomers with acrylic resins in a predetermined ratio It is possible to obtain a composition which is excellent in antistatic property, transparent, extremely low in coloration and has a very low transparency even when immersed in water: charging by further mixing a specific compound with the polyamide elastomer at a predetermined ratio. More preventive composition It can deukhal. Based on the above findings, the present invention has been completed.

Specifically, the present invention is as follows.

(A) 70 to 97% by weight of acrylic resin, (B) 3 to 30% by weight of one or more polyamide elastomers, and (C) 0 to 10% by weight of one or more electrolytes selected from organic sulfonates and organic phosphates Where (B) consists of (a) a polyamide segment and (b) a polyether segment, wherein the content of component (a) is from 25 to 60% by weight and component (b) is from 30 to 99% by weight An acrylic resin composition is provided comprising a polyoxyethylene moiety and consisting of a polyoxyalkylene moiety having a number average molecular weight of 500 to 4000.

Best Mode for Carrying Out the Invention

The present invention is described in detail below.

In the composition of the present invention, as the acrylic resin used as component (A), homopolymers or copolymers of alkyl ester compounds such as methyl, ethyl, propyl or butyl esters of (meth) acrylic acid are exemplified, for example, poly (Methyl methacrylate), poly (ethyl methacrylate), poly (propyl methacrylate), poly (butyl methacrylate), poly (methyl acrylate), poly (ethyl acrylate), methyl methacrylate-methyl acrylate Copolymers, methyl methacrylate-ethyl methacrylate copolymer, methyl methacrylate-butyl methacrylate copolymer, and methyl methacrylate-ethyl acrylate copolymer. The said acrylic resin can be used individually or in combination of 2 or more. The manufacturing method of the said acrylic resin is not specifically limited, The acrylic resin obtained by the usual suspension polymerization method, an emulsion polymerization method, a bulk polymerization method, etc. can be used suitably.

In the present invention, the polyamide segments used as segment (a) in the polyamide elastomer used as component (B) are, for example, aminocarboxylic acids or lactams having 6 or more carbon atoms, and / or diamines having 4 or more carbon atoms, and One or more monomers capable of producing polyamides, such as salts of dicarboxylic acids, and polymers obtained from dicarboxylic acids or diamines as linking agents. Examples of monomers capable of producing polyamides include, for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminoferronic acid, ω-aminocapric acid, 11-aminoound Cansan, 12-aminododecanoic acid, caprolactam, enanthlactam, capryllactam, laulactam, hexamethylenediamine-adipicate, hexamethylenediamine-sebacrate, hexamethylenediamine-dodecanedicarboxylate, Hexamethylenediamine-isophthalate and hexamethylenediamine-terephthalate. In particular, ω-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, caprolactam, laulactam, hexamethylenediamine-adipic acid salt, hexamethylenediamine-sebacate and the like are preferably used. . These can be used individually or in combination of 2 or more.

Polyamides as hard segments are related to the heat resistance, strength, hardness and affinity with acrylic resins of the elastomers, and the content of polyamides in the elastomers is 25 to 60% by weight (i.e., polyether segments as segment (b)). 75 to 40% by weight), preferably 25 to 45% by weight. When the content is less than 25% by weight, the antistatic property is lowered by kneading the elastomer with the acrylic resin. If the content exceeds 60% by weight, the affinity for kneading the elastomer with the acrylic resin is poor and the transparency is lowered.

The number average molecular weight of the polyamide segment is usually selected in the range of 400 to 3000, preferably 500 to 1200. If the number average molecular weight is less than 400, the melting point is low and the heat resistance of the resulting composition is low. When a number average molecular weight exceeds 3000, there exists a tendency for transparency of a composition to fall. Thus, both of these number average molecular weights are undesirable.

As a polyamide elastomer (class) as a component (B) used for this invention, the polyamide elastomer (class) of the following general formula (1) and / or (2) is preferable:

Is a polyether segment and n is a natural number.

The polyether segment as segment (b) is a polyoxyalkylene residue derived from polyoxyethylene residues derived from polyoxyethylene whose both ends are modified with amino groups, and other polyoxyalkylenes whose both ends are modified with amino groups. Or polyoxyalkylene moieties derived from polyoxyethylene residues derived from polyoxyethylene glycol and other polyoxyalkylene glycols. Usually, it is sufficient to select glycol in consideration of the availability of raw materials. For example, the following glycol can be used.

That is, glycols constituting polyoxyalkylene moieties derived from polyoxyalkylene glycols include, for example, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol and polyoxyethylene-polyoxypropylene block air. Coalescing is used. Moreover, the copolymer obtained by copolymerizing butanediol, propylene glycol, neopentyl glycol, hydroquinone, etc. can also be used as an ether component.

Among these glycols, in particular polyoxyethylene glycol and combinations of polyoxytetramethylene glycol or polyoxypropylene glycol, polyoxyethylene-polyoxypropylene block copolymers, and polyoxyethylene-polyoxypropylene block copolymers and polyoxyethylene glycol Is preferred, since it is possible to form transparent elastomers in a relatively wide range of ratios. Particular preference is given to a combination of polyoxyethylene glycol and polyoxytetramethylene glycol.

Among the glycols, polyoxyalkylene glycols except polyoxyethylene glycol have an effect of appropriately reducing the hydrophilicity of the resulting elastomer, and the hydrophilicity can be controlled by selecting the amount of polyoxyalkylene glycol. It is preferable to select the amount of polyoxyalkylene glycol such that the% of polyoxyethylene glycol is adjusted to 99 to 30% by weight, particularly preferably 95 to 50% by weight, based on the total weight of glycol of the present invention. When the amount of ethylene glycol exceeds 99% by weight, the acrylic resin composition obtained by using the resulting elastomer has low stability under hygroscopic conditions and antistatic property decreases with increase in haze number. If the amount is less than 30% by weight, it becomes difficult to obtain a transparent elastomer and the ability to impart antistatic property is lowered. Therefore, this is not desirable.

The number average molecular weight of the total glycol should be in the range of 500 to 4000, and the number average molecular weight of each glycol should be selected such that the number average molecular weight of the total glycol was adjusted to the above range by selecting the ratio of glycol. When the number average molecular weight is less than 500, the number average molecular weight of the polyamide segment as the hard segment in the elastomer decreases, so that the melting point of the resulting elastomer is low and therefore difficult to set. On the other hand, when number average molecular weight exceeds 4000, formation of a transparent elastomer becomes difficult.

As at least one group for linking the polyamide segment (a) to the polyether segment (b), an amide group, an ester group, or a combination of amide groups and ester groups may be present. Dicarboxylic acid or diamine can be used as a linking agent. The dicarboxylic acid may be aliphatic dicarboxylic acid or aromatic dicarboxylic acid. In the above dicarboxylic acid,

Examples include adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, and cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more. Polyamide elastomers having a high molecular weight can be obtained by using the above-mentioned glycol and substantially animal amount of dicarboxylic acid.

There is no particular limitation on the method for producing the polyamide elastomer described above, and any method can be used as long as a homogeneous and transparent elastomer can be obtained. For example, the above-mentioned monomers (classes) capable of producing polyamides, glycols and dicarboxylic acids (classes) in a proportion such that the amounts of glycol and dicarboxylic acids (classes) are substantially animal amounts to each other are mixed and These are preferably 150 to 300 ° C., more preferably 180 to 280, while removing the water in the polymer generated from the reaction by passing nitrogen gas through the reaction system or reducing the pressure to about 700 to 300 Torr. It is possible to use a process consisting of polymerization in the presence or absence of a solvent at a temperature in the range of < RTI ID = 0.0 > In this process, the use of a dehydration-condensation catalyst such as titanium alkoxide or zirconium alkoxide in dehydration-condensation is advantageous because the reaction time can be reduced and the coloring of the polymer can be prevented. Since the catalysts tend to be deactivated in the presence of water, it is advantageous to remove the water in the reaction system from the system simultaneously with the elimination of unreacted monomers (streams) capable of producing amides, followed by addition of the catalyst. By this addition in this way, a high degree of polymerization can be achieved within a short time, and a transparent polyamide elastomer having extremely low coloration can be obtained.

As a solvent which can be used, the solvent which has a very high affinity with both a polyamide segment and a polyether segment, such as N-methyl caprolactam, N-methyl- 2 pyrrolidone, a sulfolane, etc. is used preferably.

The polyamide elastomer used in the composition of the present invention preferably has a transparency with a haze number of less than 50% at a thickness of 1 mm. When the haze number exceeds 50%, the transparency of the resulting composition tends to be lowered.

The degree of polymerization of the polyamide elastomer used in the composition of the present invention may vary as necessary. The relative viscosity of the elastomeric solution in m-cresol with an elastomer concentration of 0.5 w / v% is preferably at least 1.5 when measured at a temperature of 30 ° C. When the relative viscosity is less than 1.5, the mechanical properties of the elastomer are It is poor, and when an elastomer is kneaded with acrylic resin, there exists a tendency for the mechanical property of a composition to become inadequate. Preferred relative viscosity is 1.6 or more.

In addition, various heat stabilizers such as heat aging inhibitors and antioxidants can be used to enhance the heat stability of the resulting polyamide elastomer. The heat stabilizer may be added at any stage of the initial, middle and end of the polymerization. They may also be added when the polyamide elastomer is kneaded into an acrylic resin.

As the heat stabilizer, for example, 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4 hydroxybenzyl) benzene, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxycinnaamide), 4, 4'-bis (2, 6-di-t-butylphenol), 2, 2'-methylenebis (4-ethyl- 6-t-butylphenol), pentaerythryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenol) propionate], etc. Aromatic amines such as bis (β-naphthyl) -p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, poly (2,2,4-trimethyl-1,2-dihydroquinoline) and the like Sulfur compounds such as dilaurylthiodipropionate and the like; and phosphoric acid compounds such as tris (2,4-di-t-butyphenyl) phosphite and the like.

The composition of the present invention, the composition may contain an acrylic resin in an amount of 70 to 97% by weight, preferably 80 to 95% by weight, more preferably 85 to 95% by weight, and 3 to 30 polyamide elastomer By mixing the above-mentioned acrylic resin as component (A) and polyamide elastomer as component (B) so as to contain in an amount of% by weight, preferably 5 to 20% by weight, more preferably 5 to 15% by weight. Obtained. If the mixing ratio of component (B) is less than 3% by weight, a sufficient antistatic effect cannot be obtained. If the mixing ratio exceeds 30% by weight, the rigidity tends to be lowered.

The acrylic resin composition obtained as above is excellent in antistatic property and transparency. In particular, when the composition is used as a transparent acrylic resin composition, it is preferable to use a composition having a haze number of 15% or less at a thickness of 2 mm.

In the resin composition of the present invention, a method comprising kneading a mixture of component (A) and component (B) using a conventional method such as a Benbury mixer, mixing roll, single screw or twin screw extruder, etc. Can be used. In the above case, at the kneading temperature, the kneading is preferably performed in the range of 180 to 280 ° C.

In the present invention, organic sulfonates and organic phosphates can be used as component (C) to exert further antistatic effects. Examples of the organic sulfonate and organic phosphate salt include aromatic sulfonic acids such as dodecylbenzenesulfonic acid, p-toluenesulfonic acid, dodecylphenol ether disulfonic acid, naphthalenesulfonic acid and the like: alkylsulfonic acids such as laurylsulfonic acid and the like; And alkali metal salts and alkaline earth metal salts of organic phosphoric acid such as diphenyl phosphite, diphenyl phosphate and the like. Of these, alkali metal salts are preferred, and sodium salts and potassium salts are particularly preferred.

As a component (C), the said component can be used individually or in combination of 2 or more. The content of component (C) is selected in the range of 0.05 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 2.0% by weight. When the content exceeds 10% by weight, unfavorable situations are caused, such as a decrease in rigidity, moldings of the composition on the surface roughness or coloring during molding.

In the resin composition of the present invention, other components, such as dyes, ultraviolet absorbers, weathering agents, heat stabilizers, antioxidants, lubricants, plasticizers, mold release agents, polyoxyethylene glycol and others, provided that the other components do not lower the physical properties of the resin composition. The polymer of can be mixed in any stage, such as kneading step or molding step.

The acrylic resin composition of the present invention obtained as described above may be molded by known methods generally used for molding thermoplastic resins, for example, injection molding, extrusion molding, blow molding and vacuum molding.

The present invention relates to a novel antistatic transparent acrylic resin composition, in particular having good permanent antistatic properties, inexpensive, good transparency, for example electrical appliances such as nameplates and meter covers of lighting fixtures, machines and equipment The present invention relates to an acrylic resin composition suitable as a material capable of preventing electrostatic charging in various parts such as home appliances and OA devices.

The invention is illustrated in more detail below by the following examples, although the invention is not limited thereto.

The properties of the composition and the elastomer were measured according to the following method.

(1) relative viscosity of elastomer

Measure in m − cresol under conditions of 30 ° C. and 0.5 w / v%.

(2) haze number of elastomer

The elastomer was held between polycarbonate transparent films (made by Teijin Chemical Co., Ltd., Panlite sheet) having a thickness of 0.4 mm to prepare an elastomer sheet having a thickness of 1 mm, and the whole including the polycarbonate sheet. The haze number of an elastomeric sheet is measured according to JIS K-7105 with a haze meter (made by Nippon Denshoku Co., Ltd.).

(3) surface resistivity of the composition

Using a molded sample of 50 × 50 × 2 mm, using a electrometer TR8651 and an electrode (manufactured by Advantest Co., Ltd.) and a shielding box and an electrode holder (manufactured by Ando Electric Co., Ltd.) The surface resistivity is obtained by measuring the resistance value when a voltage is applied.

(4) Total light transmittance and haze number of the composition

It measures by the method of JISK-7105 with a haze meter (made by Nippon Denshoku Co., Ltd.) using a 50x50x2 mm molded sample.

(5) yellowness of the composition

Using a molded sample of 50 × 50 × 2 mm, a colorimetric color difference meter (manufactured by Nippon Denshoku Co., Ltd.) was measured by a transmission method according to the method described in JIS K-710.

(6) flexural modulus of the composition

Measure at 23 ° C. and 55% RH in accordance with ASTM D-790 using test specimens 1/8 inch thick.

Preparation Example 1 Preparation of Polyamide Elastomer (A-1)

10 liter SUS reactor equipped with a stirrer, nitrogen inlet, distillation line and catalyst inlet port, 2240 g polyoxyethylene glycol with a number average molecular weight of 1490, 560 g polyoxytetramethylene glycol with a number average molecular weight of 1830, 301 g of terephthalic acid, capro Inject 1250 g of lactam and 8 g of 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4 hydroxybenzyl) benzene and nitrogen at a rate of 100 ml / min The reaction was carried out at 220 ° C. for 2 hours while passing, followed by 2 hours at 250 ° C. while passing nitrogen at a rate of 1000 ml / min. The pressure was then gradually reduced to distill unreacted caprolactam, then a solution of 8 g of tetrabutoxy zirconium in 50 g of caprolactam was added to the reaction system via a catalyst port and the resulting mixture was stirred at 250 ° C. and 1 Torr for 3 hours. React for a while. The molten polymer is extracted in water from the bottom of the reactor onto the strand, cooled and cut with a pelletizer to give a transparent polyamide elastomer chip.

The elastomer has a polyether segment content of 70%, a polyether ethylene glycol content of 80%, a haze number of 9% and a relative viscosity of 1.9.

Preparation Example 2

1980 g polyoxyethylene glycol having a number average molecular weight of 1490, 500 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 267 g of terephthalic acid, 550 g of 12-aminododecanoic acid and 1, 3, 5 in the same reactor as in Preparation Example 1 8 g of trimethyl-2,4,6-tris (3,5-di-t-butyl-4 hydroxybenzyl) benzene were injected and passed through nitrogen at 100 ml / min for 2 hours at 250 ° C. Carry out the reaction. In addition, 1160 g of caprolactam was added and the reaction was carried out at 250 ° C. for 3 hours while passing the nitrogen through the resulting mixture at a rate of 1000 ml / min. The pressure was then gradually reduced to distill off the unreacted caprolactam, and then a solution of 8 g of tetrabutoxy zirconium in 50 g of caprolactam was added to the reaction system via a catalyst port, and the reaction was carried out at 250 ° C. and 1 torr for 3 hours. do. Next, the same treatment as described in Preparation Example 1 is carried out to obtain a chip of polyamide elastomer (A-2).

The elastomer has a polyether segment of 62%, a polyether segment of 80% polyoxyethylene glycol, a haze number of 6% and a relative viscosity of 2.0.

Preparation Example 3

2050 g of polyoxyethylene glycol having a number average molecular weight of 1490, 510 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 335 g of sebacic acid, 1520 g of caprolactam, and hexamethylenediamine adipate in the same reactor used in Preparation Example 1 43 g and 8 g of 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene were injected and passed through nitrogen at a rate of 1000 ml / min. The reaction is carried out at 250 ° C. for 3 hours. Then, the pressure was gradually reduced to distill off the unreacted caprolactam, and then a solution of 8 g of tetrabutoxy zirconium in 50 g of caprolactam was added to the reaction system through a catalyst port, and the resulting mixture was heated at 240 ° C. and 1 Torr for 4 hours. React for a while. Next, the same treatment as described in Preparation Example 1 was carried out to obtain a chip of polyamide elastomer (A-3).

The elastomer has a polyether segment of 64%, a polyether segment of 80% polyoxyethylene glycol, a haze number of 7% and a relative viscosity of 2.1.

Preparation Example 4 Preparation of Polyamide Elastomer (A-4)

1920 g polyoxyethylene glycol having a number average molecular weight of 1490, 480 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, adipic acid 239 g, caprolactam 1750 g, hexamethylenediamine adipic acid 117 g and pentaerythryl-tetrakis [3-(3,5-di-t-butyl-4 hydroxyphenyl) propionate] 8 g were injected and 250 was passed through nitrogen at a rate of 1000 ml / min. The reaction is carried out for 3 hours at < RTI ID = 0.0 > Next, the same procedure as described in Preparation Example 1 was carried out to obtain a chip of polyamide elastomer (A-4).

The elastomer has a polyether segment of 59%, a polyether segment of 80% polyoxyethylene glycol, a haze number of 11% and a relative viscosity of 2.1.

Preparation Example 5 Preparation of Polyamide Elastomer (A-5)

In a 500 ml glass reactor equipped with a stirrer, a nitrogen inlet, and a distillation tube, 64.0 g of polyoxyethylene glycol having a number average molecular weight of 1490, 64.0 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 15.8 g of sebacic acid, and caprolactam 77.5 g, hexamethylenediamine adipate 2.0 g and pentaerythritol-tetrakis [3-(3,5-di-t-butyl-4 hydroxyphenyl) propionate] 0.4 g were injected and nitrogen The reaction is carried out at 260 ° C. for 4 hours while passing through at a rate of 90 ml / min. The pressure is then gradually reduced to distill unreacted caprolactam and then returned to atmospheric pressure, after which 0.4 g of tetrabutoxy zirconium is added and the resulting mixture is reacted at 260 ° C. and 1 Torr for 1.0 h. The molten polymer is extracted in water from the bottom of the reactor onto the strand, cooled and cut with a pelletizer to give a transparent polyamide elastomer chip (A-5).

The elastomer has 63% polyether segment content, 50% polyoxyethylene glycol content of polyether segment, 9% haze number and 2.1 relative viscosity.

Preparation Example 6 Preparation of Polyamide Elastomer (A-6)

134 g of polyoxyethylene-polyoxypropylene glycol block copolymer having a number average molecular weight of 3330 ("PLONON # 204" manufactured by Nippon Oil & Pat Co., Ltd.), 8.2 g of sebacic acid, 85 g of caprolactam, and pentaerythritol-tetra Polyamide elastomer chip (A-) in the same manner as in Production Example 5, except that 0.4 g of KISS [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was injected. 6) is obtained.

The elastomer has a polyether segment of 67%, a polyether segment of 40% polyoxyethylene glycol, a haze of 15% and a relative viscosity of 2.1.

Preparation Example 7 Preparation of Polyamide Elastomer (A-7)

88 g of polyoxyethylene glycol having a number average molecular weight of 993, 22 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 20.5 g of sebacic acid, 81.0 g of hexamethylenediamine adipate, Antimony trioxide 0.06 g, N-methyl-2-pyrrolidone 100 g and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 hydroxybenzyl) benzene 0.4 g is injected and the reaction is carried out at 200 ° C. for 1 hour while passing nitrogen at a rate of 10 ml / min. Next, the reaction is carried out at 260 ° C. for 3 hours while passing nitrogen at a rate of 90 ml / min, and then the pressure is reduced to distill off the solvent. After the pressure was returned to atmospheric pressure, 0.4 g of tetrabutoxy zirconium was added and the resulting mixture was reacted at 260 ° C. and 1 Torr for 2.0 h. Thereafter, the same treatment as described in Preparation Example 5 was carried out to obtain a polyamide elastomer chip (A-7).

The content of the polyether segment of the elastomer is 55%, the polyoxyethylene glycol content of the polyether segment is 80%, the haze number is 12%, and the relative viscosity is 1.8.

Preparation Example 8 Preparation of Polyamide Elastomer (A-8)

104 g of polyoxyethylene glycol having a number average molecular weight of 1490, 26 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 24.25 g of sebacic acid, 51.8 g of hexamethylenediamine sebacate, 0.06 g of antimony trioxide, N-methyl-2 Preparation example, except that 100 g of pyrrolidone and 0.4 g of 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4 hydroxybenzyl) benzene were injected In the same manner as in 7, a polyamide elastomer chip (A-8) is obtained.

The content of the polyether segment of the elastomer is 65%, the polyoxyethylene glycol content of the polyether segment is 80%, the haze number is 10% and the relative viscosity is 2.0.

Preparation Example 9 Preparation of Polyamide Elastomer (A-9)

85 g of polyoxyethylene glycol having a number average molecular weight of 1490, 21 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 13.8 g of sebacic acid, 88 g of 11-aminoundecanoic acid, 0.06 g of antimony trioxide, N-methyl-2-pi In Preparation Example 7, except that 100 g of ralidone and 0.4 g of 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 hydroxybenzyl) benzene were injected In the same manner as the polyamide elastomer chip (A-9) is obtained.

The content of the polyether segment of the elastomer is 53%, the polyoxyethylene glycol content of the polyether segment is 80%, the haze number is 9%, and the relative viscosity is 1.9.

Preparation Example 10 Preparation of Polyamide Elastomer (A-10)

96 g of polyoxyethylene glycol having a number average molecular weight of 1490, 24 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 17.8 g of dodecanedicarboxylic acid, and 12-aminododecanoic acid in the same reactor as used in Preparation Example 5 g and 0.4 g of 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 hydroxybenzyl) benzene were injected and nitrogen was added at a rate of 10 ml / min. The reaction is carried out at 200 ° C. for 1 hour while passing. Next, the reaction was carried out at 260 ° C. for 1 hour while passing nitrogen at a rate of 90 ml / min, and then the pressure was reduced to distill the generated water. After the pressure was returned to atmospheric pressure, 0.4 g of tetrabutoxy zirconium was added and the resulting mixture was reacted at 260 ° C. and 1 Torr for 1.0 h. Next, the same treatment as described in Preparation Example 5 was carried out to obtain a polyamide elastomer chip (A-10).

The content of the polyether segment of the elastomer is 60%, the polyoxyethylene glycol content of the polyether segment is 80%, the haze number is 4% and the relative viscosity is 2.2.

Preparation Example 11 Preparation of Polyamide Elastomer (A-11)

80 g of polyoxyethylene glycol having a number average molecular weight of 1490, 20 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 14.8 g of dodecanedicarboxylic acid, 92.8 g of 12-aminododecanoic acid, and 1, 3, 5-trimethyl- Polyamide elastomer chip (A-) in the same manner as in Production Example 10, except that 0.4 g of 2,4,6-tris (3,5-di-t-butyl-4 hydroxybenzyl) benzene was injected. 11) is obtained.

The content of the polyether segment of the elastomer is 50%, the polyoxyethylene glycol content of the polyether segment is 80%, the haze number is 5% and the relative viscosity is 2.1.

Preparation Example 12 Preparation of Polyamide Elastomer (A-12)

140 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 12.7 g of terephthalic acid, 66 g of caprolactam and 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydride Polyamide elastomer chip (A-12) was obtained in the same manner as in Production Example 5, except that 0.4 g of oxybenzyl) benzene was injected.

The elastomer has a content of 68% of a polyether segment containing no polyoxyethylene glycol, a haze number of 6% and a relative viscosity of 1.9.

Preparation Example 13 Preparation of Polyamide Elastomer (A-13)

110 g of polyoxyethylene glycol having a number average molecular weight of 993, 22.5 g of sebacic acid, 78.3 g of hexamethylenediamine adipate, 0.06 g of antimony trioxide, 100 g of N-methyl-2-pyrrolidone and 1, 3, 5-trimethyl Polyamide elastomer chip (A) in the same manner as in Preparation Example 7, except that 0.4 g of 2, 4, 6-tris (3, 5-di-t-butyl-4 hydroxybenzyl) benzene was injected. -13) is obtained.

The polyether segment of the elastomer is produced from polyethylene glycol only, the polyoxyethylene content of the polyether segment in the elastomer is 55%, the haze number of the elastomer is 15% and the relative viscosity is 1.8.

Preparation Example 14 Preparation of Polyamide Elastomer (A-14)

130 g of polyoxyethylene glycol having a number average molecular weight of 1490, 17.7 g of sebacic acid, 58.3 g of hexamethylenediamine sebaxate, 0.06 g of antimony trioxide, 100 g of N-methyl-2-pyrrolidone and 1, 3, 5-trimethyl Polyamide elastomer chip (A) in the same manner as in Preparation Example 7, except that 0.4 g of 2, 4, 6-tris (3, 5-di-t-butyl-4 hydroxybenzyl) benzene was injected. -14) is obtained.

The polyether segment of the elastomer is produced from polyoxyethylene glycol only, the content of the polyether segment in the elastomer is 65%, the haze number of the elastomer is 11% and the relative viscosity is 2.0.

Preparation Example 15 Preparation of Polyamide Elastomer (A-15)

120 g of polyoxyethylene glycol having a number average molecular weight of 1490, 18.7 g of dodecanedicarboxylic acid, 67.0 g of 12-aminododecanoic acid and 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di A polyamide elastomer chip (A-15) was obtained in the same manner as in Production Example 10, except that 0.4 g of t-butyl-4 hydroxybenzyl) benzene was injected.

The polyether segment of the elastomer is produced from polyoxyethylene glycol only, the content of polyether segment in the elastomer is 60%, the haze number of the elastomer is 4%, and the relative viscosity is 2.2.

Preparation Example 16 Preparation of Polyamide Elastomer (A-16)

2560 g of polyoxyethylene glycol having a number average molecular weight of 1490, 348 g of sebacic acid, 1500 g of caprolactam, 45 g of hexamethylenediamine adipate and 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di) A polyamide elastomer chip (A-16) was obtained in the same manner as in Preparation Example 3, except that 8 g of t-butyl-4 hydroxybenzyl) benzene was injected.

The polyether segment of the elastomer is produced from polyoxyethylene glycol only, the content of polyether segment in the elastomer is 64%, the haze number of the elastomer is 8% and the relative viscosity is 2.1.

Preparation Example 17 Preparation of Polyamide Elastomer (A-17)

2800 g of polyoxyethylene glycol having a number average molecular weight of 1980, 272 g of trimellitic anhydride, 1330 g of caprolactam and 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4) The polymerization was carried out in the same manner as in Preparation Example 3 except that 8 g of hydroxybenzyl) benzene was injected. The resulting polymer is then extracted in water from the bottom of the reactor in the form of strands, cooled with a chill roll, and the recovered strands are cut with a pelletizer to obtain chips of polyamide elastomer (A-17).

The polyether segment of the elastomer is produced from polyoxyethylene glycol only, the content of the polyether segment in the elastomer is 71%, the haze number of the elastomer is 8% and the relative viscosity is 2.3.

Preparation Example 18 Preparation of Polyamide Elastomer (A-18)

94 g of polyoxyethylene ("IYONET Y400" manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 4000 with an amine residue at each terminal in the same reactor as used in Preparation Example 5, polyoxy having a number average molecular weight of 100 40 g of tetramethylene glycol, 50 g of N-methyl-ε-caprolactam and 0.4 g of 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene Is injected and heated at 100 ° C. to perform dissolution. Subsequently, 12.2 g of sebacic acid and 65.8 g of caprolactam are added, and the reaction is carried out at 200 ° C. for 1 hour while passing nitrogen at a rate of 10 ml / min. The reaction is then carried out at 260 ° C. for 4 hours while passing nitrogen at a rate of 90 ml / min, after which the pressure is reduced to distill off the solvent and a small amount of caprolactam. After the pressure was returned to atmospheric pressure, 0.4 g of tetrabutoxy zirconium was added and the resulting mixture was reacted at 260 ° C. and 1 Torr for 2.0 h. Next, the same treatment as described in Preparation Example 5 was carried out to obtain a polyamide elastomer chip (A-18).

The content of the polyether segment of the elastomer is 67%, the polyoxyethylene glycol residue content of the polyether segment is 70%, the haze number is 13%, and the relative viscosity is 1.9.

Examples 1-15 and Comparative Examples 1-10

Each strand prepared by kneading the components in the proportions shown in Tables 1 and 2 at 230 ° C or 250 ° C by a single screw extruder is cooled with water and pelletized. The resulting pellets are then dried and injection molded at a cylinder temperature of 230 ° C. or 250 ° C. and a mold temperature of 60 ° C.

The molded samples are left at 23 ° C. and 55% RH for 2 days and then their properties are measured. Moreover, transparency (haze number) after immersing the said molded article in water of 23 degreeC for 1 day is measured. The results are shown in Tables 3 and 4.

The symbol of the acrylic resin and the additive used in the Example and the comparative example has the meaning described below. The temperature in each parenthesis is a cylinder temperature at the time of kneading and injection of a composition.

<Acrylic resin>

B-1: acrylic resin, DELPET 60 N (manufactured by Asahi Chemical Industries, Ltd.): Copolymer resin composed of 90 wt% of methyl methacrylate units and 10 wt% of methyl acrylate units (230 ° C.)

B-2: copolymer resin consisting of 85% by weight of methyl methacrylate unit and 15% by weight of ethyl acrylate unit (230 ° C)

B-3: acrylic resin, DELPET , 80 N (manufactured by Asahi Chemical Industries, Ltd.): Copolymer resin composed of 97.5 wt% of methyl methacrylate unit and 2.5 wt% of methyl acrylate unit (230 ° C.)

B-4: acrylic resin, DELPET , LP-1 (manufactured by Asahi Chemical Industries Co., Ltd.): Copolymer resin composed of 94% by weight of methyl methacrylate units and 6% by weight of methyl acrylate units (250 ° C)

<Additive>

C-1: sodium dodecylbenzenesulfonate

C-2: dodecyldiphenylether disulfonate

C-3: Sodium Diphenyl Phosphate

TABLE 1

TABLE 2

TABLE 3

TABLE 4

Industrial availability

The acrylic resin composition of the present invention contains an acrylic resin, a hard polyamide elastomer, and a transparent polyamide elastomer having a specific ratio in a specific ratio, and optionally one or more electrolytes. When immersed in water, the transparency is extremely low, the coloring is extremely small, and it is inexpensive. The composition can be suitably used as a material capable of preventing electrostatic charging in various parts such as electrical appliances, home appliances, OA appliances, such as nameplates and meter covers of lighting fixtures, machines and equipment.

Claims (5)

(A) 70 to 97% by weight of acrylic resin, (B) 3 to 30% by weight of one or more polyamide elastomers, and (C) 0 to 10% by weight of one paper electrolyte selected from organic sulfonate and organophosphate Wherein component (B) consists of (a) a polyamide segment and (b) a polyether segment, wherein the content of (a) is from 25 to 60% by weight and component (b) is from 30 to 99% by weight An acrylic resin composition containing a polyoxyethylene moiety and comprising a polyoxyalkylene moiety having a number average molecular weight of 500 to 4000. The acrylic resin composition according to claim 1, wherein the polyamide elastomer (s) used as component (B) is represented by the following general formulas (1) and / or (2): Is a polyether segment and n is a natural number. The polyamide segment according to claim 1, wherein the polyamide segment used as component (a) is an aminocarboxylic acid or lactam having 6 or more carbon atoms, and / or a salt of diamine and dicarboxylic acid having 4 or more carbon atoms, and adipic acid as a linking agent. Acrylic resin composition produced from a polymer obtained from at least one dicarboxylic acid selected from sebacic acid, dodecanedicarboxylic acid and terephthalic acid. The polyoxyalkylene moiety other than polyoxyethylene according to claim 1, which constitutes a polyether segment used as component (b), is polyoxypropylene, polyoxytetramethylene, polyoxyhexamethylene, polyoxyethylene-poly Acrylic resin compositions which are residues, such as an oxypropylene glycol copolymer. The acrylic resin composition according to claim 1, wherein the polyoxyalkylene residues except polyoxyethylene are polyoxytetramethylene residues.