JPH06286078A - Antistatic acrylic resin laminated sheet - Google Patents

Abstract

PURPOSE:To improve permanent antistatic properties and transparency and to improve weather resistance with less coloring and a low-cost by laminating a resin composition in which specific pts.wt. of acrylic resin, transparent polyamide elastomer and vinylidene fluoride polymer, organic sulfonate and organic phosphate are added on an acrylic resin board. CONSTITUTION:A mixed diol containing polyamide forming amine mixture containing 35-94 pts.wt. of acrylic resin and 50wt.% or more of caprolactam, 30-99wt.% of polyoxyethyleneglycol having 6-20C dicarboxylic acid and 500-4000 of number-average molecular weight, and 1-70wt.% of diol having the same molecular weight is polycondensed. 3-25 pts.wt. of transparent polyamide elastomer containing 55-75wt.% of a content of an ingredient and 3-40 pts.wt. of vinylidene fluoride polymer are mixed, and additive resin composition selected from organic sulfonate and organic phosphate are laminated in thickness of 3mum on an acrylic resin board.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel antistatic acrylic resin composition, and more specifically, it has excellent permanent antistatic property and transparency and excellent weather resistance, for example, lighting equipment and equipment. Acrylic resin laminated sheet suitable as a material capable of preventing static electricity on various parts such as nameplates, meter covers and other electronic products, home electric appliances, office automation equipment, signboards, store equipment, displays, front plates of various devices Is.

[0002]

2. Description of the Related Art Conventionally, since acrylic resins have excellent transparency, weather resistance, rigidity, etc., they are used for various parts such as electronic products, home appliances, office automation equipment, signboards, store equipment, displays, and various devices. Widely used as a material for front plates.

However, since this acrylic resin has a high surface resistivity and is easily charged by friction or the like, dust or dirt adheres to the outer appearance or causes troubles due to static electricity in electronic equipment parts. It has drawbacks. Therefore, it has been desired to develop a material that retains the excellent properties of the acrylic resin and has an antistatic property.

Generally, as a method for imparting antistatic performance to an acrylic resin, for example, a method of kneading a surfactant or coating it on the surface is well known.
In such a method, the surfactant existing on the surface is easily removed by washing with water or rubbing, and it is difficult to impart a permanent antistatic property.

As a method for imparting a permanent antistatic property, (1) a vinyl copolymer having a polyoxyethylene chain and a sulfonate, carboxylate or quaternary ammonium salt structure is kneaded with an acrylic resin. Method (JP-A-55-36237, JP-A-63-637)
39), and (2) polyether ester amide as a methyl methacrylate-butadiene-styrene copolymer (M
BS resin) and methyl methacrylate-acrylonitrile-
A method of kneading with a butadiene-styrene copolymer (MABS resin) (Japanese Patent Laid-Open No. 62-119256) and the like have been proposed. Other than that, (3) a polyamide elastomer and a carboxyl group, an epoxy group, an amino group are added to the acrylic resin. , A modified vinyl polymer containing at least one functional group such as a hydroxyl group, and a permanent antistatic resin excellent in surface gloss without delamination formed by further adding a rubber graft copolymer as required. ing. (JP-A-1-308444)

However, in the above method (1), since the vinyl copolymer to be blended uses a special vinyl monomer, the acrylic resin blended with this cannot avoid inevitably increasing the cost and is particularly effective. If the blending amount of the vinyl copolymer is increased in order to sufficiently exert the above, there is a drawback that the heat resistance and the like inherent in the acrylic resin is lowered. On the other hand, in the above method (2), it is necessary to maintain the transparency of the obtained composition by setting the refractive index difference between the amorphous polyetheresteramide and the MBS resin or MABS resin to 0.02 or less. Therefore, the degree of freedom in the combination of the components used is small, and polymethyl methacrylate, which is a typical acrylic resin, has a large difference in refractive index, resulting in a drawback of impairing transparency.

Since the antistatic resin (3) is a mixture of an acrylic resin and a polyamide elastomer that is incompatible with the acrylic resin, a modified vinyl polymer containing a functional group is used in combination to improve the compatibility and form a layered structure. Although it prevents peeling and imparts an antistatic effect, it is not always satisfactory because of a decrease in transparency.

As described above, the acrylic resin is excellent in transparency, but when a high molecular compound is kneaded to impart a permanent antistatic property to the acrylic resin, the high molecular compound is obtained. Transparency is often compromised due to lack of compatibility. If an attempt is made to obtain a material with good transparency, a sufficient antistatic effect may not be obtained,
The heat resistance may decrease. Furthermore, if a polymer compound having a special structure for exerting an antistatic effect without impairing the physical properties is used, the cost becomes high, and a general-purpose acrylic resin having an antistatic property cannot be obtained.

Therefore, in the field of acrylic resins, it has been desired to develop an acrylic resin material which has excellent permanent antistatic properties, is inexpensive, and has good transparency.

The present inventors have previously developed an inexpensive acrylic resin composition having excellent permanent antistatic properties, good transparency and very little coloration (Japanese Patent Laid-Open No. 4-552).
No. 26), when this acrylic resin is laminated with a substrate to form a laminated sheet, the weather resistance is not always satisfactory, and further improvement is needed.

[0011]

Under these circumstances, the present invention has excellent permanent antistatic properties, good transparency, very little coloring, and is inexpensive.
The purpose of the present invention is to provide a novel antistatic acrylic resin laminated sheet having further improved weather resistance.

[0012]

As a result of intensive studies to develop an acrylic resin laminated sheet having excellent physical properties, the present inventors have found that an acrylic resin, a specific polyamide elastomer and a vinylidene fluoride-based heavy sheet. An acrylic resin composition containing a combination with a predetermined ratio, or an acrylic resin composition obtained by further mixing this with an organic sulfonate or an organic phosphate in a predetermined ratio is laminated on an acrylic resin substrate. As a result, they have found that the object can be achieved, and have completed the present invention based on this finding.

That is, the present invention relates to (A) 35 to 94 parts by weight of an acrylic resin, (B) (a) a caprolactam alone or a mixture of amines for forming a polyamide containing at least 50% by weight of caprolactam, and (b) a carbon number. 6-20
Dicarboxylic acid and (C) number average molecular weight of 500 to 400
30 to 99% by weight of polyoxyethylene glycol having 0, other polyoxyalkylene glycol and α, ω
-Selected from hydroxy hydrocarbons, number average molecular weight 5
At least one diol having from 00 to 4000 1-7
The content of the component (C) obtained by polycondensation with a mixed diol consisting of 0% by weight is 55 to 75% by weight, and the temperature is 3
Transparent polyamide elastomer 3 having a relative viscosity of 1.5 or more at 0 ° C. and a haze value of 50% or less at a thickness of 1 mm
25 parts by weight and (C) vinylidene fluoride polymer 3 to 4
0 parts by weight is added so that the total amount becomes 100 parts by weight, and if desired, at least one compound selected from the group (D) organic sulfonate and organic phosphate is added thereto. A resin composition added in an amount of not more than 3 parts by weight is used for at least 3 parts on one surface or both surfaces of the acrylic resin substrate.
It is intended to provide an antistatic acrylic resin laminated sheet characterized by being laminated in a thickness of μm.

In the resin composition constituting the laminated sheet of the present invention, as the acrylic resin as the component (A), polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate is used. , Polyethyl acrylate, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-ethyl methacrylate copolymer, methyl methacrylate-
Examples thereof include a homopolymer or a copolymer of (meth) acrylic acid ester such as a butyl methacrylate copolymer and a methyl methacrylate-ethyl acrylate copolymer.
These acrylic resins may be used alone or in combination of two or more. Further, the production method is not particularly limited, and those produced by a known suspension polymerization method, emulsion polymerization method, bulk polymerization method or the like can be used.

The polyamide elastomer used as the component (B) in this resin composition is composed of (a) caprolactam or a polyamide-forming amine mixture containing caprolactam, (b) dicarboxylic acid, and (c) a mixed diol. Obtained by polycondensation, a polyamide portion having a carboxyl group at both ends constituting a hard segment formed from the component (a) and the component (b),
It is a multi-block type copolymer in which the diol portion constituting the soft segment is linked by an ester bond.

As the above-mentioned component (a), caprolactam alone may be used, or a mixture of caprolactam and an amine component other than caprolactam having a polyamide-forming ability may be used. The amine component having a polyamide-forming ability other than caprolactam used in the case of the mixture may be any one as long as it is used together with the dicarboxylic acid in the production of polyamide. Examples thereof include lactams such as lauryllactam, ω-aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminoundecanoic acid, hexamethylenediamine-adipate, hexamethylenediamine-sebacate. Hexamethylenediamine-dodecanedioate,
Examples thereof include diamine-dicarboxylic acid addition salts such as hexamethylenediamine-isophthalic acid salt, which may be used alone or in combination of two or more kinds. When caprolactam and other amide-forming amines are used together, a different structure is introduced into the polyamide segment, improving the transparency of the elastomer, lowering the melting point, preventing crystallization of the polyamide segment, and blending with an acrylic resin. It brings effects such as improvement of fluidity. In this case, the content of caprolactam in the polyamide-forming amine mixture should be 50% by weight or more in order to sufficiently exhibit the transparency of the obtained elastomer, the affinity with the acrylic resin, and the antistatic property. It is necessary, and it is preferable to increase the amount as the molecular weight of the diol as the component (c) increases and the content of the polyamide segment increases. Generally, it is desirable that the content of caprolactam in the polyamide-forming amine mixture is 70% by weight or more, though it depends on the molecular weight of the diol. Further, when hexamethylenediamine-adipate is used as a copolymerization component, the transparency tends to decrease, so that the content of caprolactam in the polyamide-forming amine mixture is preferably 70% by weight or more. Even if the amount of modification is the same, if the molecular weight of the diols of component (c) increases, the molecular weight of polyhexamethylene adipamide also tends to increase, and the transparency tends to decrease. In this case, it is preferable to use hexamethylenediamine-adipic acid salt in an equimolar amount or less with the diol of the component (c).

The dicarboxylic acid having 6 to 20 carbon atoms as the component (b) may be an aliphatic carboxylic acid or an aromatic dicarboxylic acid. Examples thereof include adipic acid, sebacic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid and cyclohexanedicarboxylic acid, which may be used alone or in combination of two or more. Good. A high molecular weight polyamide elastomer can be obtained by using the dicarboxylic acid as the component (b) in substantially equimolar amounts with the diols as the component (c).

The polyamide as the hard segment is related to the heat resistance, strength, hardness of the elastomer and the affinity with the acrylic resin, and the content in the elastomer is 25 to 45% by weight, that is, (c) It is necessary that the content of the diols as a component is in the range of 75 to 55% by weight, and preferably in the range of 30 to 40% by weight. If this content is less than 25% by weight, the antistatic property when kneaded with an acrylic resin becomes insufficient, and if it exceeds 45% by weight, the affinity when kneaded with an acrylic resin becomes poor and the transparency decreases. To do.

The number average molecular weight of this polyamide segment is usually 400 to 1500, preferably 500 to 1.
It is good to choose in the range of 200. This number average molecular weight is 40
If it is less than 0, the melting point is low, and the heat resistance of the resulting composition is inferior. If it exceeds 1500, the transparency of the composition tends to decrease, which is not preferable.

The mixed diol of the component (c) is a mixture of polyoxyethylene glycol and polyoxyalkylene glycol other than polyoxyethylene glycol, α, ω-dihydroxy hydrocarbon, or both. As the polyoxyalkylene glycol other than the polyoxyethylene glycol, for example, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, block copolymer glycol of ethylene oxide and propylene oxide, or the like is used. As these polyoxyalkylene glycols, those obtained by copolymerizing other diols such as butanediol, propylene glycol, neopentyl glycol and hydroquinone as an ether component can also be used. Examples of the α, ω-dihydroxy hydrocarbon include polyolefin glycol obtained by polymerizing olefin or butadiene to form a hydroxyl group at the terminal and hydrogenating its double bond, hydrogenated polybutadiene glycol, 1,3-propane. Diol,
1,4-butanediol, neopentyl glycol,
1,6-hexanediol, 1,4-bis- (hydroxymethyl) cyclohexane, dibutylene glycol and the like can be used.

Among these diols, in particular, a combination of polyoxyethylene glycol and polyoxytetramethylene glycol or polyoxypropylene glycol, and a combination of polyoxyethylene polyoxypropylene glycol block copolymer and polyoxyethylene glycol. Is preferable because a transparent elastomer can be obtained in a relatively wide range of composition ratio.

Among the above-mentioned diols, polyoxyalkylene glycols other than polyoxyene glycol or α, ω-dihydroxy hydrocarbons have the effect of appropriately reducing the hydrophilicity of the elastomer obtained, and the hydrophilicity depends on the amount. It can be adjusted, but in the present invention, it is necessary to select the amount of polyoxyene glycol in the diol mixture to be 99 to 30% by weight, and it is necessary to select it to be 95 to 50% by weight. Is more preferable. When the amount of polyoxyethylene glycol exceeds 99% by weight, the hydrophilicity cannot be sufficiently reduced, and when water is used when cooling from a high temperature state, it swells significantly and becomes sticky, which makes recovery difficult. On the other hand, if the amount is less than 30% by weight, it becomes difficult to obtain a transparent elastomer, and the ability to impart antistatic properties is also reduced.

The total number average molecular weight of these diols used as the component (c) is required to be in the range of 500 to 4000, preferably 1000 to 3000, and within this range depending on the composition ratio of each diol. It is necessary to select the number average molecular weight of each diol so that When the number average molecular weight is less than 500, the number average molecular weight of the hard segment in the elastomer becomes small, and as a result, the melting point of the obtained elastomer becomes low and it becomes difficult to solidify. On the other hand, when the number average molecular weight exceeds 4000, it becomes difficult to form a transparent elastomer.

The method for producing the polyamide elastomer as the component (B) is not particularly limited as long as it is a method capable of obtaining a homogeneous and transparent elastomer. For example, in the polymer produced by the reaction, the components (a), (b) and (c) are mixed in a ratio such that the components (b) and (c) are substantially equimolar. The amount of water is removed from the reaction system by flowing nitrogen gas into the reaction system or reducing the pressure to about 700 to 300 Torr.
It can be produced by polymerizing at a temperature of 300 ° C., preferably 180 to 280 ° C.
In this method, the reaction temperature can be raised stepwise during dehydration condensation. In the composition of the present invention, the polyamide elastomer used as the component (B) needs to have a haze value of 50% or less at a thickness of 1 mm, more preferably 40% or less,
When the haze value exceeds 50%, the transparency of the obtained composition tends to decrease.

The degree of polymerization of the polyamide elastomer used in the composition of the present invention can be varied as required, but the relative viscosity of the metacresol solution having an elastomer concentration of 0.5% by weight / volume measured at a temperature of 30 ° C. It must be 1.5 or more. If this relative viscosity is less than 1.5, the mechanical properties will be low, and when kneaded with an acrylic resin, stickiness to the roll or stain on the roll may occur. A preferable relative viscosity is 1.6 or more.

In order to improve the thermal stability of this polyamide elastomer, various heat stabilizers such as heat anti-aging agents and antioxidants can be used, and these are added at the initial stage, the middle stage and the final stage of the polymerization. To be done. It can also be added when the polyamide elastomer is kneaded with the acrylic resin.

Examples of the heat stabilizer include N, N'-
Hexamethylenebis (3,5-di-t-butyl-4-hydroxycinnamic acid amide), 4,4'-bis (2,6-
Di-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ], Various hindered phenols, N, N'-bis (β-
Naphthyl) -p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, poly (2,2,4-
Aromatic amines such as trimethyl-1,2-dihydroquinoline) and sulfur compounds such as dilaurylthiodipropionate and phosphorus compounds are used.

Examples of the vinylidene fluoride polymer used as the component (C) in the composition of the present invention include vinylidene fluoride polymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene. Copolymer, vinylidene fluoride-hexafluoroacetone copolymer, vinylidene fluoride-hexafluoroisobutene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropene copolymer, or Examples thereof include terpolymers of vinylidene fluoride and the above-mentioned copolymerizable monomers. The content of vinylidene fluoride units in each copolymer is preferably in the range of 10 to 95 mol%. The vinylidene fluoride polymer as the component (C) may be used alone or in combination of two or more kinds.

In the composition of the present invention, the acrylic resin as the component (A), the polyamide elastomer as the component (B), and the vinylidene fluoride-based polymer as the component (C) are added based on a total weight of 100 parts by weight thereof. , 35-94 respectively
It is necessary to blend in a proportion of 3 parts by weight, 3 to 25 parts by weight and 3 to 40 parts by weight, preferably 65 to 90 parts by weight, 5 to 15 parts by weight and 5 to 20 parts by weight. If the amount of component (B) is less than 3 parts by weight, a sufficient antistatic effect cannot be obtained, and if it exceeds 25 parts by weight, the rigidity decreases. Also,
If the amount of the component (C) is less than 3 parts by weight, the weather resistance is insufficient, and if it exceeds 40 parts by weight, turbidity and rough skin will be noticeable in the molded product.

In the present invention, in order to further exert the antistatic effect, an organic sulfonate or an organic phosphate can be added as the component (D), if desired. Examples of the organic sulfonate and the organic phosphate include dodecylbenzene sulfonic acid, p-toluene sulfonic acid,
Aromatic sulfonic acids such as dodecyl diphenyl ether disulfonic acid, naphthalene sulfonic acid, alkyl sulfonic acids such as lauryl sulfonic acid, diphenyl phosphite,
Examples thereof include alkali metal salts and alkaline earth metal salts of organic phosphoric acid such as diphenyl phosphate. Of these, alkali metal salts are preferable, and sodium salt and potassium salt are particularly preferable.

The component (D) may be used alone, or
You may use it in combination of 2 or more type. The amount thereof is not more than 10 parts by weight based on 100 parts by weight of the total amount of the acrylic resin of the component (A), the polyamide elastomer of the component (B) and the vinylidene fluoride polymer of the component (C), It is preferably selected in the range of 0.1 to 5 parts by weight. If this amount exceeds 10 parts by weight, the rigidity is lowered, the surface of the molded product is roughened, and the molded product is colored during molding, which is not preferable.

Next, as the substrate of the laminated sheet of the present invention,
An acrylic resin is used, and this is the same as the acrylic resin used as the component (A) of the resin composition described above, for example, polymethylmethacrylate, polyethylmethacrylate, polypropylmethacrylate, polybutylmethacrylate. , Polymethyl acrylate, polyethyl acrylate, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-ethyl methacrylate copolymer, methyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-acrylic acid A homopolymer or copolymer of (meth) acrylic acid such as an ethyl copolymer can be used. These acrylic resins may be used alone or in combination of two or more. The production method thereof is not particularly limited, and those obtained by a known suspension polymerization method, emulsion polymerization method, bulk polymerization method or the like can be used.

Surprisingly, the laminated sheet of the present invention has remarkably improved weather resistance and therefore can be used for various outdoor applications. Polyamide elastomer is generally poor in weather resistance due to the influence of polyamide, polyether, polyester segment, etc. contained in the polymer chain, but like the laminated sheet of the present invention, a resin composition containing a vinylidene fluoride polymer is used. When used, the weather resistance is improved, and in particular, surface whitening of the molded product, that is, increase in haze value is significantly suppressed.

The laminated sheet of the present invention is obtained by laminating the above resin composition on one or both sides of an acrylic resin substrate so as to have a thickness of at least 3 μm. The thickness of the laminated portion is 5 μm or more, preferably 10 μm or more. Generally 10-200
It can be used as a laminated sheet having a laminated portion of μm,
It is preferable that the thickness of the laminated portion is within 30% of the total thickness of the laminated sheet, because the physical properties are less deteriorated.

In the laminated portion and the substrate of the laminated sheet of the present invention, other components, for example, colorants such as dyes and pigments, talc, mica, calcium carbonate, magnesium carbonate and titanium dioxide are used as long as the physical properties thereof are not impaired. , Inorganic fillers such as barium sulfate and silicon dioxide, polymethylmethacrylate cross-linked products, methyl methacrylate-butadiene-styrene copolymer cross-linked products, acrylic cross-linked elastic materials having a multilayer structure, organic additives such as polystyrene cross-linked products, Various ultraviolet absorbers, antioxidants, light stabilizers, lubricants, plasticizers, release agents and the like can be added in any process such as a kneading process or a molding process.

As a method for obtaining the laminated sheet (including film) of the present invention, coextrusion is used.
Although a laminating method and a laminating method can be used, the coextrusion method can make the fluidity of both layers uniform at the time of lamination, so that the adhesion of both layers is good and the molding strain is similar. Are better. The coextrusion method is performed using two or more ordinary extruders. For example, the diameter of the base material is 40 mm, 60 m
An extruder having a diameter of 20 mm, 30 mm, 45 mm, or the like having a smaller diameter for the laminated portion is used. The resin composition having an antistatic property used in the laminated portion is prepared by blending the above-mentioned components (A), (B), (C) and optionally (D) and other additives with a blender or the like. After being uniformly kneaded, pelletized by an extruder is used.

On the other hand, in the case of the laminating method, a film made of a resin composition is prepared in advance, and a laminated sheet is prepared by superposing the film on the base material sheet at the polishing roll at the exit of the extruder. be able to. In this case, the technical point is to prevent air from entering during superposition and to improve the adhesiveness due to the roll temperature.

The laminate of the present invention can be applied to a film as well as a sheet. Control of the thickness of the laminated portion of the laminated sheet and film and the base material portion is 2 in the case of the sheet.
It can be adjusted by the extrusion amount of one or more extruders and the roll clearance of the polishing roll at the extruder outlet, and in the case of a film, it can be adjusted by the extrusion amount of two or more extruders and the roll speed of the rolls at the extruder outlet.

When producing a laminated sheet, it is important to match the fluidity of the laminated portion and the substrate. This can also be adjusted to some extent at the extruder temperature.

The thickness of the laminated portion and the whole of the extruded sheet can be almost quantified by the extrusion amount of the extruder, but in terms of measurement, the thickness is 1 m.
When the thickness is m or more, it is measured with a caliper or a micrometer, and when the thickness is 1 mm or less, the cross section of the sheet is measured by a differential interference microscope or a commercially available film thickness meter [for example, manufactured by Big Mallincklot,
PIG Universal (film thickness meter for dry film)], and when it is smaller, it can be seen with an electron microscope. Clarify the interface between the laminated part and the substrate,
Further, in order to facilitate the measurement of the thickness of the laminated portion, it is convenient to preliminarily mix a small amount of a coloring agent such as a dye with the resin of the laminated portion.

[0041]

The acrylic resin laminated sheet of the present invention is
A resin composition containing an acrylic resin, a specific polyamide elastomer, a vinylidene fluoride polymer, and optionally an organic sulfonate or an organic phosphate, laminated on an acrylic resin base material, which is excellent. In addition to having permanent antistatic property and transparency, the weather resistance is further improved. For example, various parts such as lighting equipment, equipment nameplate, meter cover, electronic products, home electric appliances, office automation equipment, etc. It is preferably used as a material capable of preventing electrostatic charging.

[0042]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

The physical properties of the composition and elastomer were evaluated according to the following methods. (1) Relative Viscosity of Elastomer Measured in meta-cresol under the conditions of 30 ° C. and 0.5% by weight / volume.

(2) Elastomer haze value A 0.4 mm thick polycarbonate transparent film [manufactured by Teijin Kasei Co., Ltd., trade name: Panlite Sheet] is sandwiched with an elastomer to prepare a sheet with an elastomer thickness of 1 mm. The haze value of each polycarbonate film was measured with a haze meter manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K-7105.

(3) Surface resistivity of composition Using a molded sample of 50 × 50 × 2 mm, an Electrometer TR8651 and electrode manufactured by Adevan Test Co., Ltd. and a shield box and electrode holder manufactured by Ando Electric Co., Ltd. were used. Then, the resistance value when 500 V was applied was measured to obtain the surface resistivity.

(4) Total light transmittance and haze value of composition Using a molded sample of 50 × 50 × 2 mm and a haze meter manufactured by Nippon Denshoku Industries Co., Ltd., the method of JISK-7105 was applied. It measured according to it.

(5) Flexural Modulus of Composition According to ASTM D-790, a test piece having a thickness of 1/8 inch was used and measured at 23 ° C. and 55% RH. In Table 2, this is referred to as elastic modulus.

(6) Evaluation of weather resistance A molded sample of 50 × 50 × 2 mm was used, and after irradiation for 1000 hours using a Sunshine Carbon Arc Weather Meter (hereinafter abbreviated as SWM) manufactured by Suga Test Instruments Co., Ltd. The haze value of the sample was evaluated by the method (4).

Reference Example 1 2020 g of polyoxyethylene glycol having a number average molecular weight of 1980 was placed in a 10-liter SUS reactor equipped with a stirrer, a nitrogen inlet, a distillation tube, and a catalyst charging pot.
860 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 248 g of terephthalic acid, 1300 g of caprolactam and pentaerythrityl-tetrakis [3
8 g of-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] was charged and reacted at 250 ° C for 3 hours while reducing the pressure to 500 Torr.

Next, the degree of pressure reduction was gradually increased to distill off unreacted caprolactam, and then a solution prepared by dissolving 8 g of tetrabutoxyzirconium in 50 g of caprolactam was charged from the catalyst pot under reduced pressure at 260 ° C. and 1 Torr. 2.
The reaction was carried out for 5 hours. The molten polymer is made into a strand from the bottom of the reactor, extracted into water, cooled, and cut with a pelletizer to make a transparent polyamide elastomer (B-
The chip of 1) was obtained. This elastomer had a soft segment content of 72% by weight, contained 70% by weight of a polyoxyethylene glycol segment, had a haze value of 8% and a relative viscosity of 2.2.

Reference Example 2 500 m equipped with a stirrer, nitrogen inlet and distilling pipe
14.0 glass reactor of polyoxyethylene glycol having a number average molecular weight of 1490 64.0g, number average molecular weight 183
0, polyoxytetramethylene glycol 64.0 g,
Sebacic acid 15.8 g, caprolactam 77.5 g, hexamethylenediamine-adipate 2.0 g and pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate]
0.4 g was charged and reacted at 260 ° C. for 4 hours while flowing nitrogen at 90 ml / min. Next, the pressure was gradually reduced to distill off unreacted caprolactam, the pressure was returned to normal pressure, 0.4 g of tetrabutoxyzirconium was added, and the mixture was reacted at 260 ° C. and 1 Torr for 1.0 hour. The molten polymer was made into a strand form from the reactor, extracted into water, cooled, and cut with a pelletizer to obtain transparent polyamide elastomer (B-2) chips. This elastomer has a soft segment content of 63% by weight, of which 50% of the polyoxyethylene glycol segment is
The content was wt%, the haze value was 9%, and the relative viscosity was 2.1.

Reference Example 3 2050 g of polyoxyethylene glycol having a number average molecular weight of 1490 and polyoxytetramethylene glycol 510 having a number average molecular weight of 1830 were placed in the same reactor as in Reference Example 1.
g, 335 g of sebacic acid, 1520 g of caprolactam,
Hexamethylenediamine-adipate 43 g and 1,
3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene 8g
250g while feeding nitrogen at 1 liter / min
The reaction was carried out at ℃ for 3 hours. Then, the degree of vacuum was gradually increased to distill off unreacted caprolactam, and then a solution of 8 g of tetrabutoxyzirconium in 50 g of caprolactam was added to the reaction system from the catalyst pot under reduced pressure.
The reaction was carried out at 1 ° C and 1 torr for 4 hours. Thereafter, a chip of polyamide elastomer (B-3) was obtained in the same manner as in Reference Example 1. This elastomer had a soft segment content of 64% by weight, a polyoxyethylene glycol segment of 80% by weight, a haze value of 7% and a relative viscosity of 2.1.

Examples 1 to 8 and Comparative Examples 1 to 4 Asahi Kasei acrylic resin pellets 80N (copolymer of methyl methacrylate and methyl acrylate) as the acrylic resin of the component (A), and a small amount of 80N colored pellets as a colorant ( Polyamide elastomer (B-1 to 3) and vinylidene fluoride polymer [trade name: Kureha KF Polymer # 1 using the color number 33140) in the blending ratio shown in Table 1.
000 (hereinafter referred to as PVDF), Kureha Chemical Industry Co., Ltd.
Manufactured by the manufacturer] and sodium dodecylbenzenesulfonate (hereinafter referred to as DBS), and 0.5 parts by weight of a hindered amine stabilizer (trade name Tinuvin 770, manufactured by Ciba Geigy) as a stabilizer, an ultraviolet absorber (trade name Tinuvin P,
0.3 parts by weight of Ciba Geigy) and 0.2 parts by weight of heat stabilizer (trade name Irgafoss 168, Ciba Geigy) were blended using a tumbler, and then a resin temperature of 250 ° C. was obtained using a vented extruder (diameter 40 mm). Melt and knead at
The resin composition was prepared by pelletizing.

Next, the pellets thus obtained were used for a laminated portion by using an extruder having a diameter of 20 mm and L / D = 32, while Asahi Kasei Delpet 80N having a diameter of 4 was used as a base material portion.
Co-extrusion was performed using an extruder with 0 mm and L / D = 32.

The die was a two-type, two-layer feed block type, the lip opening was 3.0 mm, and the extrusion temperature was 240 to 250 ° C. The thickness of the laminated sheet was adjusted mainly with the clearance of the polishing roll and the number of rotations set to 2.0 mm, and the thickness of the surface layer portion was adjusted by the discharge amount of both extruders. Thus, a sheet having a width of 50 cm was prepared. The thickness of this sheet is approximately 2.0 mm, and the thickness of the laminated portion is shown in Table 1.

[0056]

[Table 1]

For comparison, a laminated sheet having a thickness of 2.0 mm and containing no PVDF in the laminated portion in Example 1 was prepared and evaluated in the same manner as above. Further, a pellet having antistatic performance used in the laminated portion in Example 1 and Delpet 80N were used individually to prepare a single layer sheet having a thickness of 2.0 mm, which was also evaluated for comparison. The results are shown in Table 2.

[0058]

[Table 2]

Claims (2)

[Claims] 1. A polyamide-forming amine mixture containing (A) 35 to 94 parts by weight of an acrylic resin, (B) (a) caprolactam alone or at least 50% by weight of caprolactam, and (b) 6 to 20 carbon atoms. 30 to 99% by weight of dicarboxylic acid and (c) polyoxyethylene glycol having a number average molecular weight of 500 to 4000, other polyoxyalkylene glycol and α, ω-hydroxy hydrocarbon, and a number average molecular weight of 500 to 1. Obtained by polycondensation with a mixed diol consisting of 1 to 70% by weight of at least one diol having 4000, the component (C) is 55 to 75% by weight, and the relative viscosity at a temperature of 30 ° C. is 1.
Resin composition in which 3 to 25 parts by weight of a transparent polyamide elastomer having a haze value of 50% or less at a thickness of 1 mm and 5 to 5 parts by weight and 3 to 40 parts by weight of a vinylidene fluoride-based polymer (C) are blended in a total amount of 100 parts by weight. Is laminated on one side or both sides of an acrylic resin substrate with a thickness of at least 3 μm, to provide an antistatic acrylic resin laminated sheet. 2. A polyamide-forming amine mixture containing (A) 35 to 94 parts by weight of an acrylic resin, (B) (a) caprolactam alone or at least 50% by weight of caprolactam, and (b) 6 to 20 carbon atoms. 30 to 99% by weight of dicarboxylic acid and (c) polyoxyethylene glycol having a number average molecular weight of 500 to 4000, other polyoxyalkylene glycol and α, ω-hydroxy hydrocarbon, and a number average molecular weight of 500 to Obtained by polycondensing a mixed diol consisting of 1 to 70% by weight of at least one diol having 4000, the content of the component (C) is 55 to 75% by weight, and the relative viscosity at a temperature of 30 ° C. is 1.5. As described above, 3 to 25 parts by weight of a transparent polyamide elastomer having a haze value of 50% or less at a thickness of 1 mm and (C) vinylidene fluoride 3 to 40 parts by weight of the polymer is blended so that the total amount is 100 parts by weight, and 10 parts by weight of at least one compound selected from the group (D) organic sulfonate and organic phosphate. An antistatic acrylic resin laminated sheet, characterized in that the resin composition added in an amount not exceeding 10 is laminated on one surface or both surfaces of an acrylic resin substrate in a thickness of at least 3 μm.