JPH079633A - Antistatic acrylic resin laminated sheet - Google Patents

Abstract

PURPOSE:To provide an acrylic resin laminated sheet which has excellent permanent antistatic function and keeps a function proper to a base material. CONSTITUTION:An acrylic resin laminated sheet is formed by layering, on one face or both faces of a basic acrylic resin layer, a resin composition with a thickness of 5p or above consisting of a polyether ester amide (A) of 1-35wt.%, an acrylic resin (B) of 99-65wt.% and at least one kind of compound (C) of 0-5wt.% selected out of organic sulfonate and organic phosphate. In a cross section of the laminated part of the sheet in parallel with the flowing direction, dispersion index of (A) component existing as a dispersion particle is 0.2 or above.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin laminated sheet having a permanent antistatic property and having an excellent antistatic property while retaining the original performance of a base material.

[0002]

2. Description of the Related Art Polymer materials are used in a wide range of fields due to their excellent properties. If the antistatic performance can be imparted to these materials, the applications can be further expanded. For example, it is extremely useful for applications such as OA equipment nameplates, automobile instrument covers, lighting covers, displays, and projection television screens.

As a method for improving the antistatic performance of polymer materials, for example, JP-A-55-36237 and JP-A-56-120751 disclose conjugated diene and / or alkyl acrylate and alkylene oxide group. A polymer obtained by graft-polymerizing a vinyl-based monomer or a vinylidene-based monomer onto a hydrophilic rubber-like polymer obtained by copolymerization with a vinyl-based monomer having Is disclosed. In addition, JP-A-4-
Japanese Patent No. 71844 discloses an antistatic laminated sheet containing a polyether ester amide. The composition having antistatic properties used in the present invention is disclosed in JP-A-5-78543, and acrylic resins are shown as having excellent antistatic properties.

[0004]

The object of the present invention is to impart excellent antistatic performance to acrylic resins and to impart properties inherent to these resins, such as strength, rigidity, optical characteristics and impact resistance. It is an object of the present invention to provide an antistatic acrylic resin laminated sheet that does not deteriorate the properties of

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, provided a resin composition layer having a specific thickness with an antistatic property on one or both sides of an acrylic resin. Furthermore, they have found that the object can be achieved by precisely controlling the morphology of the resin composition, and have reached the present invention.

That is, according to the present invention, the polyether ester amide (A) 1 is formed on one or both sides of the acrylic resin layer of the substrate.
-35 wt%, acrylic resin (B) 99-65 wt%, and at least one compound (C) 0-5 wt% selected from organic sulfonates and organic phosphates. An acrylic resin laminated sheet in which the composition is laminated in a thickness of 5 μm or more, and the dispersion index of the component (A) present as dispersed particles is 0 in a cross section parallel to the flow direction of the laminated part of the sheet. It is the antistatic acrylic resin laminated sheet characterized by being more than 1.2.

As the composition having an antistatic property used in the laminated portion of the present invention, those described in detail in JP-A-5-78543 are used. That is, the polyether ester amide (A) used in the present invention comprises (a) a polyamide-forming monomer containing at least 50% by weight or more of caprolactam, (b) a dicarboxylic acid having 6 to 20 carbon atoms, and (C) Containing at least one diol selected from polyoxyalkylene glycol and α, ω-dihydroxy hydrocarbon, and the content of the polyoxyethylene glycol segment in the diol is 30.
~ 99 wt% and a number average molecular weight of 200 to 4
An elastomer obtained by polycondensation with a diol having a content of 000 and having a content of the component (c) of 55 to 7
5% by weight, relative viscosity at a temperature of 30 ° C. is 1.5 or more,
Also, it is a transparent elastomer having a haze number of 50% or less and a thickness of 1 mm.

Examples of polyamide-forming monomers other than the caprolactam of the component (a) which is a constituent component of the polyetheresteramide (A) include lauryllactam, 11-aminoundecanoic acid, 12-aminododecanoic acid and hexamethylenediamine. -Adipic acid salt, hexamethylenediamine-sebacic acid salt, hexamethylenediamine-dodecanedioic acid salt, hexamethylenediamine-isophthalic acid salt and the like, and these may be used alone,
You may use it in combination of 2 or more type.

The content of caprolactam in the component (a) is 5 in order to sufficiently exhibit the transparency of the obtained elastomer, the compatibility with the acrylic resin and the antistatic performance.
It is necessary to be 0% by weight or more, preferably 70%.
It is more than weight%. Polyether ester amide (A)
The dicarboxylic acid having 6 to 20 carbon atoms of the component (b) which is the other constituent component of the above may be an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid. Examples thereof include adipic acid, sebacic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, and these may be used alone or in combination of two or more. This (b)
The component dicarboxylic acid is used in a substantially equimolar amount with the diols as the component (c) described later to obtain a high molecular weight elastomer.

The polyamide as the hard segment is related to the heat resistance, strength and 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 The content of the diols as the component) is required to be in the range of 55 to 75% by weight, preferably 30 to 40% by weight. If this content is less than 25% by weight, the antistatic performance when kneaded with an acrylic resin is poor, and if it exceeds 45% by weight, the affinity is poor when kneaded with an acrylic resin and the transparency is reduced. .

Examples of the polyoxyalkylene glycol of the diol as the component (c) which is another constituent of the polyether ester amide (A) include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and polyoxyethylene glycol. Examples thereof include oxyhexamethylene glycol and a block copolymer of ethylene oxide and propylene oxide.

As the α, ω-dihydroxy hydrocarbon, for example, polyolefin glycol or hydrogenated polybutadiene glycol obtained by polymerizing olefin or butadiene to hydroxyl group the terminal and hydrogenating its double bond,
1,3-propanediol, 1,4-butanediol,
Neopentyl glycol, 1,6-hexanediol,
Etc.

Of the above diols, polyoxyalkylene glycols other than polyoxyethylene glycol or α, ω-dihydroxy hydrocarbons have the action of adjusting the hydrophilicity of the resulting elastomer. In the present invention, it is necessary to select the amount of the polyoxyethylene glycol segment in the diols to be 99 to 30% by weight, preferably 99 to 50% by weight. 99
If the amount is more than 30% by weight, the effect of lowering the hydrophilicity is insufficient, and if it is less than 30% by weight, it is difficult to obtain a transparent elastomer, and the ability to impart antistatic performance is also reduced.

The diols have a number average molecular weight of 500 to 4000, preferably 1000 to 3000.
It is necessary to be. When the number average molecular weight is less than 500, the melting point of the elastomer is lowered and it becomes difficult to solidify. If the number average molecular weight exceeds 4000, it becomes difficult to form a transparent elastomer. The method for producing the polyether esteresteramide (A) is not particularly limited as long as it is a method capable of obtaining a homogeneous and transparent elastomer. For example, the above-mentioned component (a), component (b), and (c) Component) is mixed in a ratio such that the component (b) and the component (c) are substantially equimolar, and water in the polymer produced by the reaction is passed through a nitrogen gas in the reaction system. 700-30
While removing it outside the system by reducing the pressure to about 0 Torr, preferably 150 to 300 ° C., more preferably 18
A method of polymerizing at a temperature in the range of 0 to 280 ° C can be used. The reaction temperature may be raised stepwise during the dehydration condensation.

At this time, a part of caprolactam remains unreacted, but it is preferable to remove this from the reaction mixture by distilling under reduced pressure. The reaction mixture after removing the unreacted caprolactam is optionally under reduced pressure, preferably 2
Higher polymerization can be achieved by post-polymerization at a temperature in the range of 00 to 300 ° C, more preferably 230 to 280 ° C. In this post-polymerization, it is advantageous to use a dehydration condensation catalyst such as titanium alkoxide or zirconium alkoxide because the reaction time is shortened and the coloring of the polymer can be prevented. Since these catalysts are easily deactivated in the presence of water, it is advantageous to add water after removing unreacted caprolactam and removing water in the reaction system out of the system. By doing so, a high degree of polymerization can be achieved in a short time, and a transparent polyetheresteramide having an extremely low degree of coloring can be obtained.

In the reaction method, coarse phase separation is prevented by simultaneously causing esterification and amidation in the course of dehydration condensation, whereby a homogeneous and transparent elastomer can be obtained. This elastomer has an excellent affinity with an acrylic resin and provides an antistatic effect and mechanical properties when kneaded with the acrylic resin. The polyether ester amide (A) used in the present invention has a haze number of 50% or less, preferably 40% or less at a wall thickness of 1 mm. Also, 30% of 0.5 wt% / vol% meta-cresol solution
The relative viscosity at ° C is 1.5 or more, preferably 1.6 or more.

The blending ratio of the polyether ester amide (A) in the resin composition used for the laminated portion of the present invention is 1 to 35.
% By weight, preferably 5 to 25% by weight. If it is less than 1% by weight, the antistatic performance is inferior, and if it exceeds 35% by weight, the mechanical properties, especially the flexural modulus after immersion in water are lowered, which is not preferable. Examples of the acrylic resin used for the laminated portion and the base material portion of the present invention include a resin mainly composed of methyl methacrylate as a general acrylic resin, which includes methyl methacrylate homopolymer or methyl methacrylate and methyl acrylate, ethyl acrylate, etc. Alkyl acrylate, vinyl cyanide compound, (meth) acrylic acid, vinyl pyridine, vinyl morpholine,
Vinylpyrrolidone, tetrahydrofurfuryl acrylate, N, N-dimethylamino acrylate, N, N-dimethylacrylamide, 2-hydroxy (meth) acrylate, ethylene glycol (meth) acrylate, glycerin mono (meth) acrylate, maleic anhydride,
Copolymers with any one or more of copolymerizable monomers such as aromatic vinyl compounds, impact-resistant acrylic resins, heat-resistant acrylic resins, and low hygroscopic acrylic resins are included. A rubber elastic body of impact-resistant acrylic resin is disclosed in Japanese Patent Laid-Open No.
-58554, JP-A-55-94917,
As disclosed in Japanese Patent Laid-Open No. 61-32346,
Briefly, it is a multi-stage polymer produced by a multi-step sequential polymerization method in which an elastic layer and a non-elastic layer are alternately formed around an acrylic polymer core material.

More specifically, an acrylic multi-stage structure in which a polymer elastic layer containing alkyl acrylate as a main component and a non-elastic layer containing methyl methacrylate as a main component are alternately provided around a polymer core material containing methyl methacrylate as a main component. It is a (multilayer) polymer and has an average particle size of 0.06 to 0.5.
μm is desirable. Further, an acrylic multi-stage (multi-layer) polymer having an intermediate layer in which methyl methacrylate gradually increases between the elastic layer and the non-elastic layer is also effective. The proportion of these multistage (multilayer) polymers in the impact resistant acrylic resin is 3 to 70% by weight, preferably 5 to 50% by weight.

An example of the heat-resistant acrylic resin is Japanese Patent Publication No. 6
It is described in Japanese Patent Publication No. 1-49325. A low hygroscopic acrylic resin is disclosed, for example, in JP-A-58-113214.
JP-A-59-227909 and JP-A-1-1785
No. 11, for example. In the present invention, the acrylic resin used for the laminated portion and the acrylic resin used for the base material portion may be the same or may be a combination of the above.

The compounding amount of at least one compound (C) selected from organic sulfonates and organic phosphates in the resin composition used for the laminated portion of the present invention is 0 to 5% by weight,
It is preferably 0.1 to 4% by weight. If it is used in an amount of more than 5% by weight, the surface of the surface is roughened during molding and coloring is not preferable. Examples of these are alkali metal salts or alkaline earth metal salts of aromatic sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dodecyldiphenyletherdisulfonic acid, naphthalenesulfonic acid, and a condensation product of naphthalenesulfonic acid and formalin. Examples thereof include alkali metal salts or alkaline earth metal salts of diphenyl phosphite, diphenyl phosphate and the like. Of these, sodium salts and potassium salts are particularly preferable.

In the present invention, the thickness of the laminated portion laminated on the base material portion is 5 μm or more, preferably 10 μm or more. If it is less than 5 μm, the antistatic performance is poor. The thickness may be the minimum necessary, but generally it can be used as a laminated sheet having a laminated portion of 30 to 200 μm. Preferably,
When the thickness of the laminated portion is 30% or less in the entire laminated sheet, the deterioration of physical properties may be small (in the case of double-sided lamination, the total thickness of the laminated portions on both surfaces is 30% or less of the total thickness).

In the laminated sheet of the present invention, the morphology of the polyetheresteramide (A) dispersed in the laminated part is the most important. That is, in the cross section parallel to the flow direction of the laminated portion of the laminated sheet, the dispersion index of the component (A) present as dispersed particles is 0.2 or more, preferably 0.3 or more. If the dispersion index is less than 0.2,
Poor antistatic performance. As described above, it is surprising that the morphology of the component (A) in the laminated part has a great influence on the antistatic performance, and the present invention has been reached by the discovery thereof. In order to control the morphology of the component (A) in the laminated part, the melt viscosity of the component (A) and the component (B) is appropriately controlled, and / or the temperature condition of the extruder at the time of manufacturing the laminated sheet. It is necessary to properly control the temperature condition of the polishing roll.

In the layered part and / or the base material part of the present invention, other components, such as an inorganic light diffusing agent, an organic light diffusing agent, a pigment, a dye, a reinforcing agent, are added as long as the physical properties thereof are not impaired.
Fillers, mold release agents, heat stabilizers, antioxidants, light stabilizers, UV absorbers, plasticizers, other polymers and the like can be contained in any step such as a kneading step or a molding step.

As a method for obtaining the laminated sheet (including film) of the present invention, coextrusion is used.
Method and laminating method. The co-extrusion method is excellent in that the fluidity of both layers can be matched and made uniform at the time of lamination, so that the adhesiveness of both layers is good and the molding strain is similar. For coextrusion, two or more ordinary extruders are used, and the base material portion is an extruder having 40 mmφ, 60 mmφ, 90 mmφ, etc.
In addition, the laminated part is smaller than that, 20 mmφ, 30 mm
An extruder of φ, 45 mmφ or the like is used. The resin composition having an antistatic property used in the laminated portion is prepared by mixing the above antistatic agent into the resin in advance by using a blender or the like to homogenize the resin, and then pelletizing it with an extruder.

In the case of the laminating method, a film in which an antistatic agent is kneaded is prepared in advance, and a laminated sheet is obtained by superposing this film on the base material sheet at the polishing roll section at the exit of the extruder. in this case,
The technical points are the prevention of air inclusion during stacking and the improvement of adhesion by roll temperature. The laminate of the present invention can be applied to a film as well as a sheet.

The thicknesses of the laminated portion and the base material portion of the laminated sheet are controlled by the discharge amount of two or more extruders and the roll clearance of the polishing roll at the exit of the extruder. Also, when producing a laminated sheet, it is important to match the fluidity of the laminated portion and the base material portion, and this can be specifically carried out by adjusting the temperature of the extruder.

The thickness of the laminated part and the whole of the laminated sheet can be almost quantified by the discharge amount of the extruder.
When it is 1 mm or less, the sheet cross section can be measured with a differential interference microscope or a commercially available film thickness meter, and when it is smaller, it can be seen with an electron microscope.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The evaluation and test methods used in Examples and Comparative Examples are as follows. (1) Measurement of surface resistance According to JIS-K6911, SM- manufactured by Toa Denpa Kogyo KK
Using a 10-type ultra-ultra-insulator, the direct current voltage applied between the two electrodes on the surface of the test piece was divided by the current flowing through the surface layer to express the value. The measurement was performed one day after the sample was prepared. (2) Ash adhesion test After rubbing the sample 10 times, the ash adhesion state was observed at a height of 2 cm from the cigarette ash. ◎ indicates no adhesion, ○
The mark indicates slight adhesion, and the X mark indicates large adhesion. (3) Total light transmittance Measured by an optical characteristic test method according to JIS-K7105. (4) Dispersion index Particles present within 20 μm from the surface layer were prepared by adjusting a transmission electron micrograph (photograph magnification: 30,000 times) of an ultrathin section in which a cross section parallel to the flow direction of the laminated sheet of the laminated sheet was stained with ruthenium acid The major axis and the minor axis of 100 particles randomly selected from particles having a major axis of 0.05 μm or more were measured.
Of particles with a major axis of 0.05 μm or more, major axis / minor axis ≧
The number of particles satisfying 2.0 was defined as N, and N / 100 was defined as a dispersion index.

[0029]

[Reference Example 1] Preparation of polyether ester amide In a 10-liter sus reaction vessel equipped with a stirrer, a nitrogen inlet, a distillation tube, and a catalyst charging pot, 2020 g of polyoxyethylene glycol having a number average molecular weight of 1980,
Charge 860 g of polyoxytetramethylene glycol having a number average molecular weight of 1830, 248 g of terephthalic acid, 1300 g of caprolactam, and 8 g of pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and nitrogen. Was reacted at 250 ° C. for 3 hours while flowing at 1 liter / minute.

Then, the degree of pressure reduction was gradually increased to distill off unreacted caprolactam, and then a solution of 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 was made into a strand form from the bottom of the reactor, extracted into water, cooled, and cut with a pelletizer to obtain transparent polyetheresteramide chips.

The soft segment content was 72% by weight, of which 70% by weight of polyoxyethylene glycol segment was contained, the haze number was 8%, and the relative viscosity was 2.2.
Met.

[0032]

[Reference Example 2] Preparation of resin composition for laminated part Asahi Kasei acrylic resin pellet "Delpet 80N" 8
9.5% by weight, 10% by weight of polyetheresteramide prepared in Reference Example 1, 0.5% by weight of sodium dodecylbenzenesulfonate, Sanol 770 (manufactured by Sankyo Co., Ltd.)
0.5 parts by weight, Tinuvin P (manufactured by Ciba Geigy) 0.3
Parts by weight, Irgafos 168 (manufactured by Ciba Geigy).
After blending 05 parts by weight using a tumbler, the mixture was melt-kneaded at a resin temperature of 250 ° C. with a vented 30 mmφ twin-screw extruder, and pelletized.

[0033]

[Example 1] An extruder having a diameter of 20 mm and L / D = 32 was used as the laminated portion for the pellet prepared in Reference Example 2, while the base material portion was Asahi Kasei acrylic resin pellet "Delpet 8".
0N ″ was coextruded using an extruder having a diameter of 40 mm and L / D = 32. The die was a two-layer, two-layer feed block type, the lip opening was 3.0 mm, and the extrusion temperature was 240 to 26.
The temperature was 0 ° C. and the die temperature was 230 ° C. The thickness of the laminated sheet is 2.0mm with the clearance of the polishing roll.
The thickness of the surface layer was adjusted by adjusting the discharge rate of the extruder. Thus, a sheet having a sheet width of 50 cm was produced. The thickness of the base material portion and the laminated portion of this product is 2.0 mm.
And 50 μm. The surface electrical resistance of this sample was of the order of 10 ¹⁰ Ω and there was no ash adhesion in the ash adhesion test. The dispersion index calculated from an electron micrograph of a cross section parallel to the flow direction of the laminated portion was 0.72. The results are shown in Table 1.

[0034]

Examples 2 and 3 and Comparative Examples 1 and 2 The same procedure as in Example 1 was carried out except that the die temperature was changed as shown in Table 1. The results are shown in Table 1.

[0035]

Example 4 and Comparative Example 3 Example 4 and Comparative Example 3 were carried out in the same manner as in Example 1 except that the die temperature was changed as shown in Table 1 and the discharge amount of the extruder was changed. The results are shown in Table 1.

[0036]

[Table 1]

[0037]

The acrylic resin laminated sheet of the present invention is
It is possible to effectively exhibit the antistatic effect without losing the characteristics of the base material, and it can be manufactured at low cost, and is used for the above-mentioned applications, electric equipment nameplates, automobile instrument covers, lighting covers, etc. It is extremely useful as a material.

Claims (1)

[Claims] 1. On one or both sides of an acrylic resin layer of a base material, 1 to 35% by weight of a polyether ester amide (A), 99 to 65% by weight of an acrylic resin (B), and an organic sulfonate and What is claimed is: 1. An acrylic resin laminated sheet in which a resin composition comprising 0 to 5% by weight of at least one compound (C) selected from organic phosphates is laminated in a thickness of 5 μm or more, An antistatic acrylic resin laminated sheet, wherein the dispersion index of the component (A) present as dispersed particles is 0.2 or more in a cross section parallel to the flow direction of the laminated portion.