JP2003238822A - Electroconductive resin composition, laminate and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroconductive resin composition capable of expressing a good conductivity even when the amount level of electroconductive particles added is low and to provide a laminate using the same. <P>SOLUTION: The electroconductive resin composition involves a phase (A) which contains no electroconductive particles (X) and a phase (B) which contains the electroconductive particles (X), wherein the phase (A) forms a dispersed phase in the continuous phase of the phase (B). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to a conductive resin composition useful in the field of antistatic or antistatic properties, a laminate using the same, and a method for producing the laminate. The conductive resin composition of the present invention and a laminate using the same are, for example, floor materials and wall materials for clean rooms, front plates of display devices, window glass, show window glass,
It is particularly useful in instrument cover materials, semiconductor packaging materials, and the like.

[0002]

2. Description of the Related Art Electrostatic damage is an extremely popular phenomenon not only in industry but also in general society and family life. Such electrostatic damage can be roughly classified into the following three types.

(1) Obstacles caused by static electricity itself: For example, adsorption to other charged objects (adhesion of paper, matting of clothes), disturbance of printing due to ink, etc., charging of human body (not to human body) Negative impact on electronic circuits.

(2) Failure caused by discharge due to static electricity:
For example, malfunction of electric circuit, ignition of gas, liquid / powder, etc., shock shock to human body (cracking discharge of clothes, shock when touching doorknob).

(3) Obstacles due to adsorption of dust and the like due to static electricity: For example, dirt on an object due to adsorption of dust and the like (black stain on a plastic bag).

The above-described antistatic technology (an antistatic technology, a removal technology) for preventing a failure due to static electricity is a technology that has existed for a long time, but recently, its importance is further increasing.

This is because, due to the spread of synthetic fibers and plastics, which are easily charged with static electricity, and the decrease in indoor humidity due to cooling and heating, the modern industrial society or general society is in an environment where static electricity is more likely to occur. is there.

Particularly, with the recent development and sophistication of the electronics industry (semiconductor manufacturing apparatus and related equipment) represented by personal computers, facsimiles, etc.,
In the fields related to the electronics industry, as well as in a wide range of fields that require a "clean environment" such as electronics, electricity, medicine, food, precision machinery, and biotechnology, the problem of static electricity has been greatly highlighted.

For example, in a sheet or film used for a floor material / wall material in a clean room of a semiconductor factory, a front plate of a display device, a window glass, a show window glass, an instrument cover material, and a semiconductor packaging material, etc. It is extremely important to prevent floating dust attached by static electricity from becoming a pollution source in a clean room.

Various antistatic sheets or films have been proposed in the past for the purpose of preventing contamination by such static electricity. For example, in JP-A-7-310033 and JP-A-11-203942, surface resistance can be obtained by providing a layer in which conductive fine particles having a particle size sufficiently smaller than the wavelength of light are dispersed on the surface of a sheet or film. Is disclosed.

In these methods, as the conductive fine particles,
50 wt% (mass%) or more of tin-doped indium oxide fine particles and antimony-doped tin oxide are added in the antistatic coating film, and the resistance value of the surface of the sheet or film obtained by this method is 10 ⁶ to 10 ⁷ Ω /
□ It is about.

Further, in Japanese Patent Laid-Open No. 2001-131485, an easily dispersible low-boiling solvent of a conductive oxide fine particle and a highly dispersible high-boiling solvent are used in a conductive coating, and a mesh of the conductive fine particles is formed on a resin surface. It is described that by forming a coating film having openings, a coating film containing 20 wt% (mass%) of tin oxide fine particles can provide a resin plate having a surface resistivity of about 10 ¹⁰ Ω / □. There is.

[0013]

However, in these conventionally known antistatic sheets or films, the conductive fine particles having a low addition amount of 30 wt% (mass%) or less do not exceed 10 ⁸ Ω / □. A good surface resistance value has not yet been developed.

In the methods disclosed in the above-mentioned JP-A-7-310033 and JP-A-11-203942, 50 wt% (mass%) is contained in the antistatic coating film on the surface.
The above expensive conductive fine particles are used. This is 10
^{Although this} is an effective method for exhibiting a conductivity of ⁸ Ω / □ or less, it tends to increase the manufacturing cost of the antistatic sheet or film and cause deterioration of the transparency and strength of the coating film. Furthermore, since it is necessary to disperse a large amount of conductive particles in these films and the like, there are drawbacks that the difficulty of production thereof increases and the storage stability of the obtained conductive paint is poor. .

On the other hand, the above-mentioned Japanese Patent Laid-Open No. 2001-1314
Regarding Japanese Patent Publication No. 85, it is possible to develop a surface resistivity of about 10 ¹⁰ Ω / □ by using a method of forming a mesh opening in the coating film by using a small amount of tin oxide fine particles. It is difficult to develop a surface resistivity of 10 ⁸ Ω / □ or less. In addition, the definition of the easily dispersible low-boiling point solvent and the highly dispersible high-boiling point solvent of the conductive oxide fine particles in this technique is ambiguous, and therefore it is not always easy to select the combination. Further, such a conductive paint is easily affected by the coating conditions when the solvent is volatilized, and changes in quality during storage, so that it is difficult to always exhibit the same performance.

An object of the present invention is to provide a conductive resin composition and a laminate using the same, in which the above-mentioned drawbacks of the prior art are eliminated.

Another object of the present invention is to provide a conductive resin composition capable of exhibiting good conductivity even when the conductive particles are added in a small amount, and a laminate using the same. It is in.

Another object of the present invention is to provide a conductive resin composition excellent in transparency and surface smoothness and a method for producing a laminate using the same.

[0019]

Means for Solving the Problems As a result of intensive studies, the present inventor did not actively disperse conductive particles in a resin composition as in the prior art, but rather positively proposed a dispersed phase containing no conductive particles. It has been found that it is extremely effective to achieve the above-mentioned object by intentionally introducing it into the resin composition (that is, by positively imparting a certain degree of non-uniformity).

The conductive resin composition of the present invention is based on the above findings, and more specifically, the phase (A) containing no conductive particles (X) and the phase (A) containing no conductive particles (X) ( A conductive resin composition containing B); a phase (A) containing no conductive particles (X) forms a dispersed phase in a continuous phase of a phase (B) containing conductive particles (X). It is characterized by doing.

According to the present invention, there is further provided a laminate comprising a base material; and a layer containing the conductive resin composition disposed on the base material; and wherein the conductive resin composition is conductive. Containing a phase (A) containing no conductive particles (X) and a phase (B) containing conductive particles (X); and a conductive phase (B) containing conductive particles (X) in a continuous phase. Provided is a laminate characterized in that the phase (A) containing no functional particles (X) forms a dispersed phase.

According to the present invention, there is further provided a method for producing the above-mentioned laminate having good transparency and smooth surface.

In the conductive resin composition of the present invention having the above-mentioned constitution, a small amount of conductive particles are used by arranging the conductive particles to an appropriately nonuniform degree (for example, in a network). Even if it is 10 ⁸ Ω / □
It is easy to develop the following conductivity.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically with reference to the drawings as necessary. In the following description, "part" and "%" representing the quantitative ratio are based on mass unless otherwise specified.

(Resin Composition) In terms of morphology, the resin composition of the present invention contains the conductive particles (X) in the continuous phase of the phase (B) containing the conductive particles (X). The phase (A) which does not contain forms a dispersed phase.

In general, when the conductive particles in the conductive resin composition are substantially completely dispersed as primary particles, electricity flows between adjacent conductive particles (resin is present). It is not preferable because it does not exist. On the contrary, the degree of dispersion is low,
Even when the conductive particles are aggregated, the conductive path is not formed and the conductivity is not substantially exhibited.

On the other hand, as in the present invention, when the conductive particles are appropriately dispersed in the conductive resin composition, the conductive particles are connected to each other to form a morphology having a network-like continuous structure. Since it is easily treated, it exhibits suitable conductivity.

In the embodiment of the present invention in which the phase (B) containing the conductive particles (X) forms a continuous mesh structure in the conductive resin composition, a relatively large amount of conductive particles is contained. Since substantially the same effect as in the case where the particles are appropriately dispersed is exhibited, good conductivity can be exhibited even when a small amount of conductive particles is used.

As described above, the conductive resin composition of the present invention contains the phase (A) containing no conductive particles (X) and the phase (B) containing the conductive particles (X).

(Phase Containing Conductive Particles) The phase (B) containing the conductive particles (X) is the conductive particles (X).
The embodiment containing is not particularly limited. From the viewpoint of exhibiting good conductivity by adding a small amount of conductive fine particles, the conductive particle-containing phase (B) has a network-like continuous structure in which conductive particles are connected to each other, It is preferable to include the functional particles (X).

(Resin Binder) The resin binder constituting the phase (B) containing the conductive particles (X) is not particularly limited as long as the conductive particles (X) can be contained therein. As this resin binder, a resin binder generally used for paints and inks can be preferably used. As the resin binder, for example, solvent-based or water-based thermoplastic, thermosetting, or radiation curable resins such as acrylic, polyester, urethane, and silicone resins can be preferably used.

Among these resin binders, from the viewpoint of scratch resistance, a resin binder containing a cured product of a thermosetting or radiation curable compound containing a compound having two or more polymerizable groups is preferable. Further, from the viewpoint of transparency and weather resistance of the conductive resin composition, a resin binder containing a cured product of a thermosetting or radiation curable compound containing an acrylic compound having two or more polymerizable groups is preferable. .

Examples of the acrylic compound having two or more such polymerizable groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and triethylene glycol di (meth).
Acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis [4-acryloxydiethoxyphenyl] propane, 2,2-bis [4-methacryloxydiethoxyphenyl] propane, 3-phenoxy-2 -Difunctional (meth) acrylates such as propanoyl acrylate, 1,6-hexanediol diacrylate, 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether; Data Ellis Le Thor tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris - (2-hydroxyethyl) - isocyanurate (meth) trifunctional acrylates such as (meth)
Acrylate: pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned.

Further, a phosphazene (meth) acrylate compound in which at least two (meth) acryloyloxy groups are introduced into the phosphazene ring of the phosphazene compound, and at least two (meth) acryloyloxy groups are introduced into the molecule. A urethane (meth) acrylate compound, a polyester (meth) acrylate compound having at least two (meth) acryloyloxy groups introduced into the molecule, and the like can also be preferably used.

Malonic acid / trimethylolethane /
A mixed polyester compound of (meth) acrylic acid containing one or two (meth) acryloyloxy groups in the molecule by a combination of compounds such as (meth) acrylic acid can also be preferably used. The compounds suitable for these resin binders can be used alone, but may be a mixture of two or more kinds.

(Reactive Diluent) The above-mentioned thermosetting or radiation-curable compound may contain a reactive diluent in addition to the above, if necessary. Examples of such reactive diluents include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Butyl acrylate, n-hexyl (meth) acrylate,
Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth)
Examples thereof include compounds having a (meth) acryloyloxy group such as acrylate, 1,4-butanediol mono (meth) acrylate, hydroxystyrene, and hydroxy-terminated polyethylene glycol styryl ether.

In addition to these, it has an unsaturated double bond in the molecule of styrene, methylstyrene, chlorostyrene, bromostyrene, vinyltoluene, divinylbenzene, vinyl acetate, N-vinylcaprolactam, N-vinylpyrrolidone and the like. Compounds other than (meth) acrylate can also be suitably used as the reactive diluent.

The radiation to be used when curing the radiation-curable compound means infrared rays, visible rays, ultraviolet rays, X-rays, electron rays, α rays, β rays, γ rays and the like.

From the viewpoint of the hardness of the surface of the conductive resin composition,
The amount of the reactive diluent used is preferably 0 to 70 parts, more preferably 0 to 50 parts, relative to 100 parts of the radiation curable compound.

(Conductive Particles) The continuous phase (B) in the conductive resin composition of the present invention contains conductive particles (X). Such conductive particles are not particularly limited as long as they have conductivity. As the conductive particles, for example, those used in ordinary conductive paints can be used without particular limitation.
More specifically, as conductive particles, metal-based powders such as gold, silver, copper and nickel; carbon-based powders such as furnace black, acetylene black, Ketjen black and graphite;
Typical examples include oxides, nitrides, and carbides containing tin, titanium, zinc, aluminum, silicon, antimony, indium, and the like as elements, or inorganic powders of two or more kinds of these compounds, or a mixture thereof. Of course, organic systems such as polyacetylene and polypyrrole can also be used. These conductive particles can be used in various shapes such as powder, flakes and fibers.

Among these, tin-doped indium oxide fine particles and antimony-doped tin oxide fine particles are particularly preferable from the viewpoint of transparency. The most preferable are tin-doped indium oxide fine particles having excellent conductivity. Such tin-doped indium oxide powder is commercially available as, for example, Pastran ITO type-B manufactured by Mitsui Kinzoku Co., Ltd.

From the viewpoint of transparency and conductivity of the conductive resin composition, the upper limit of the average particle diameter of the conductive particles (X) is preferably 200 nm or less, particularly preferably 100 nm or less, Most preferably, it is 50 nm or less. On the other hand, the lower limit is preferably 5 nm or more,
It is particularly preferably 10 nm or more, and most preferably 1
It is 0 nm or more. Transparency if the average particle size is too large,
The conductivity and the dispersion stability may be reduced, and when the average particle size is too small, the dispersion stability of the conductive particles (X) in the conductive resin composition may be deteriorated.
The average particle size can be measured by a laser diffraction / scattering method using a Microtrac particle size analyzer (X-100, manufactured by Nikkiso Co., Ltd.).

From the viewpoint of the conductivity of the conductive resin composition, the conductive particles (X) are contained in the phase (B) containing the conductive particles (X) at 7% by volume as 100 × X / B. It is preferably contained in the above ratio, and more preferably 10% by volume or more. Most preferably, this volume ratio is 10% by volume or more. On the other hand, the upper limit is preferably 40% by volume or less, particularly 3
It is more preferable that the content is 0% by volume or less. Most preferably, this volume ratio is 25% by volume or less.

If the proportion of the conductive particles (X) in the phase (B) containing the conductive particles (X) is too small,
The continuous phase of the phase (B) containing the conductive particles (X) tends to be difficult to exhibit sufficient conductivity. On the other hand, if the proportion of the conductive particles (X) is too large, the moldability and strength of the conductive resin composition tend to decrease, and the manufacturing cost tends to increase.

If necessary, such conductive particles may be surface-treated with a known surface-treating agent such as a silane coupling agent.

(Phase containing no conductive particles) A phase (A) containing no conductive particles (X) constituting the conductive resin composition of the present invention together with the above-mentioned conductive particle-containing phase (B).
Is not particularly limited as long as it can form a dispersed phase in the continuous phase (B). As such a dispersed phase (A),
The type and composition are not limited, and organic and / or inorganic compounds can be used.

The organic compound may be the same as or different from the above resin binder component usable as the phase (B) containing the conductive particles (X).

As the above-mentioned inorganic compound, an inorganic substance different from the conductive particles (X) such as alumina, silica, titania, zirconia, ceria, iron oxide and manganese oxide can be used. These organic and / or inorganic compounds may be used alone or in combination of two or more as required.

The lower limit of the diameter of the phase (A) containing no conductive particles (X) is preferably 200 nm or more, more preferably 300 nm or more, particularly preferably 3 nm.
It is 50 nm or more. On the other hand, the upper limit is preferably 10 μm or less, more preferably 5 μm or less,
It is particularly preferably 3 μm or less. If the minimum diameter of the phase (A) that does not contain the conductive particles (X) is too small, the conductivity will decrease, and if it is too large, the strength of the coating film will tend to be impaired.

The volume ratio (for example, 100 × A / (A + B)) of the phase (A) containing no conductive particles (X) in the conductive resin composition is preferably 30% by volume or more. , And more preferably 35% by volume or more. The ratio of the conductive particles (X) to the entire conductive resin composition (for example, 100 × X / (A + B)) is
It is preferably 1 to 14% by volume, more preferably 2 to 8% by volume.

If the volume ratio of the phase (A) not containing the conductive particles (X) in the conductive resin composition is too small, the morphology of the conductive resin composition will change to the conductive particles (X).
Has a structure similar to that uniformly dispersed, and the network of conductive paths tends to be not efficiently formed.
Therefore, in order to develop the desired conductivity,
As a result, more conductive particles (X) must be used, and the manufacturing cost of the conductive resin composition tends to increase. On the other hand, if the volume ratio of the phase (A) containing no conductive particles (X) in the conductive resin composition is too large, the strength of the coating film tends to be impaired.

(Formation Method) The formation method of the continuous phase of the phase (B) containing the conductive particles (X) and the dispersed phase of the phase (A) containing no conductive particles (X) is not particularly limited.

In the present invention, a suitable forming method is, for example, the phase separation behavior of the resin component,
A method of forming a dispersed phase of the phase (A) containing no conductive particles (X) can be mentioned. It is more preferable to use a method of adding particles forming the non-containing phase (A) to the phase (B) containing the conductive particles (X).

As the additive particles forming the non-containing phase (A), resin particles or inorganic particles can be used alone, or two or more kinds can be used in combination, and an organic-inorganic composite obtained by combining them can be used. Particles can also be used.

The additive particles forming the non-containing phase (A) may not be substantially dissolved in the coexistence of the resin binder, the organic solvent and the like constituting the phase (B) containing the conductive particles (X). preferable.

The additive particles forming the non-containing phase (A) are substantially combined with the phase (B) containing the conductive particles (X) in order to impart excellent transparency to the resin composition of the present invention. It is preferable to have a similar refractive index. Here, with respect to “having substantially the same refractive index”, the refractive index n _{A at} 589 nm of the additive particles forming the non-containing phase (A) and the phase (B) containing the conductive particles (X) are described. ), The absolute value of the difference from the refractive index n _{B at} 589 nm | n _A −n _B | is 0.20.
Hereafter, it is more preferably 0.10 or less. The refractive index was measured at 25 ° C. using an Abbe refractometer (Digital Abbe refractometer DR-A1 manufactured by Atago Co., Ltd.).

Commercially available products may be used as the non-containing phase (A) particles, for example, MX-150 (acrylic crosslinked resin particles, average particle size 1.5 μm, manufactured by Soken Chemical Industry Co., Ltd.), Eposter S-12. (Melamine / formaldehyde condensate particles, average particle size 1-2 μm, manufactured by Nippon Shokubai Co., Ltd.), Seahoster KE-P50 (silica particles, average particle size 0.5
μm, manufactured by Nippon Shokubai Co., Ltd., and the like.

From the viewpoint of dispersibility in the conductive resin composition, such non-containing phase (A) particles may be surface-treated with a known surface treatment agent such as a silane coupling agent, if necessary. May be.

(Additive) The conductive resin composition of the present invention contains at least a phase (A) containing no conductive particles (X) and a phase (B) containing conductive particles (X). However, in the range that does not substantially impair the properties of the conductive resin composition of the present invention as necessary, various additives, for example, photoinitiators, thermosetting catalysts, antioxidants, dispersion aids, colorants, UV absorbers, photosensitizers, light stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, filler antiaging agents, wettability improvers , One or more selected from coating surface improvers and the like.

As the above-mentioned photoinitiator, for example, a usual photopolymerization initiator such as a phenylketone compound or a benzophenone compound can be used.
4 "(manufactured by Nippon Ciba Geigy)," Irgacure 9 "
07 "(manufactured by Nippon Ciba-Geigy Co., Ltd.)," Darocur 1
Commercially available products such as "173" (manufactured by Merck Japan Co., Ltd.) and "Ezure KIP100F" (manufactured by Japan Sebel Hegner Co., Ltd.) can be used. In the present invention, the photoinitiator, based on the mass of the entire conductive resin composition,
It is preferable to use 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.

Examples of the above-mentioned photosensitizer include benzoin, benzoin ethyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, azobisisobutyronitrile. , Benzoyl peroxide, and other commonly known photosensitizers. In the present invention, the photosensitizer is based on the total mass of the conductive resin composition,
It is preferable to use 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.

(Form of Composition) The conductive resin composition of the present invention can be used to form a film or sheet by itself, but from the viewpoint of transparency and cost, it may be formed on the surface of another substrate. By forming it as a coating film (coating), it can be used as a laminate. Here, the thickness of the coating film made of the conductive resin composition of the present invention is 0.1 to 5
The thickness is preferably 0 μm, particularly preferably 0.5 to 30 μm. If the coating film is too thick, its transparency tends to decrease.

(Substrate) The type of substrate on which the coating film made of the conductive resin composition is to be formed is not particularly limited. From the viewpoint of transparency of the laminate, for example, glass, acrylic resin, polycarbonate resin, polystyrene, styrene-
A plate, a sheet, a film, etc. containing a synthetic resin such as an acrylic copolymer, a polyolefin such as polyethylene or polypropylene, or the like can be preferably used.

(Laminating Method) The method for forming the layer containing the conductive resin composition of the present invention, or the method for laminating on the surface of the substrate is not particularly limited. In the embodiment in which the conductive resin composition is laminated on a substrate, for example, a coating agent prepared by dissolving the above-mentioned conductive resin composition or a precursor thereof in a suitable solvent is coated on the substrate, A method of drying and / or curing can be suitably used if necessary. In the present invention,
A coating agent prepared by dissolving the conductive resin composition or its precursor in an appropriate solvent as necessary is referred to as a "composition for forming a film of the conductive resin composition".

Examples of such a solvent include water, alcohols such as diacetone alcohol, methanol, ethanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone,
Representative examples thereof include aromatics such as toluene and xylene, esters such as ethyl acetate, and the like.

In the method for producing the coating agent, a paint shaker, a ball mill, a sand mill, a three-roll mill, an attritor, a homomixer, or the like can be used to disperse the conductive particles.

As a coating method, a general method can be used. For example, bar coater, flow coater,
It can be applied by a roll coater, a spray gun, a spin coating method, a dipping coating method, or the like.
When a radiation curable resin is used as the resin binder, it may be polymerized and cured by irradiation with radiation after coating.

(Molding) In the present invention, the laminate having the layer containing the conductive resin composition may be molded by using, for example, a casting polymerization mold or a molding mold. In this method, for example, a layer containing a conductive resin composition is formed on the surface of a casting polymerization mold or a molding die, and then contacted with the layer, the polymerizable compound is cast polymerized, or a molten resin is molded. By doing so, a plastic molded product may be formed, and the layer may be transferred to the surface of the plastic molded product.

By such a method, when a molding die or casting polymerization mold having an arbitrary surface shape is used, a laminate having that shape can be obtained, and a molding or casting mold having a particularly smooth surface is obtained. When the polymerization type is used, it is possible to obtain a laminate having a smooth surface.

The casting polymerization method applicable to such an embodiment of the present invention is not particularly limited, but for example, a casting polymer made of glass or the like containing a methyl methacrylate monomer containing a partial polymer called syrup is used. A so-called cast polymerization method of injecting into a polymerization type and polymerizing and curing is included.

(Cast Polymerization Method) When this cast polymerization method is used, the composition for forming a film of the conductive resin composition is applied to the inner surface of the glass mold and dried or / and polymerized to give a conductive property. After forming a film of the resin composition in advance, cast polymerization of methyl methacrylate syrup can be performed inside the glass casting polymerization mold.

The method for producing or assembling the glass casting polymerization mold made of this glass plate is not particularly limited, but for example, a gasket (soft polyvinyl chloride, ethylene-vinyl acetate copolymer, polyethylene, ethylene- (Methyl methacrylate copolymer etc.) is inserted and fixed or clamped with a clamp,
Can be assembled.

(Continuous Cast Polymerization) As a continuous cast polymerization method, there is known a method of casting polymerization of methyl methacrylate or the like between two steel belts. In the case of using, the method of the present invention can be carried out, for example, by forming a film of the conductive resin composition on the surface of the steel belt.

A polymerization apparatus comprising a pair of endless belts which face each other at a predetermined interval and which can be suitably used in the continuous cast polymerization method is known, for example, from Japanese Patent Publication No. 46-41602. Device. A specific example of such an endless belt polymerization apparatus is shown in FIG.

In FIG. 3, a main pulley 3 and a pair of endless belts 1 and 2 arranged vertically are respectively provided.
The tension is given by 4, 5, and 6, and the endless belts 1 and 2 are moved so as to run at the same speed by arrows a.
Direction, and the direction of arrow b. The upper and lower paired carrier rolls 7 are running endless belts 1, 2
Support horizontally.

Thus, the pair of endless belts 1, 2
While the belt is running, the composition for forming a conductive curable liquid film is applied to the belt 2 from the position 15, and then the film-forming composition thus applied is applied to a predetermined film thickness with a film thickness adjusting roll 18. To Then, the film forming composition is dried in the drying zone 16 and polymerized and cured by the high pressure mercury lamp 17 to form a film of the film forming composition on the belt 2.

On the other hand, the polymerizable raw material is the raw material injection device 14,
It is supplied between the pair of endless belts 1 and 2. The vicinity of both end portions of the pair of endless belts 1 and 2 is sealed by two elastic gaskets 12.

By treating the polymerizable raw material in this manner, the polymerizable raw material is heated by the hot water spray 9 in the first polymerization zone 8 to be polymerized as the endless belts 1 and 2 travel, and then the second polymerization is performed. In the zone 10, it is heated by the far infrared heater to complete the polymerization of the polymerizable raw material. The polymerized product is then cooled in the cooling zone 11 and then converted into the plate-shaped polymer 13 as the endless belts 1, 2
Taken from.

There are no particular restrictions on the polymerizable raw material used in casting polymerization, but for example, from the viewpoint of transparency of the polymerization product,
A syrup containing a monomer containing methyl methacrylate as a main component or a small amount of a polymer can be preferably used. Here, “having methyl methacrylate as a main component” means “containing 50% by mass or more of methyl methacrylate”.

In a syrup containing a monomer containing methyl methacrylate as a main component or a small amount of a polymer to be used for such a purpose, in addition to methyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid Acrylic esters such as propyl and butyl acrylate, cyclohexyl methacrylate, phenyl methacrylate, methacrylic acid esters such as benzyl methacrylate, styrene,
Aromatic vinyl compounds such as α-methylstyrene and p-methylstyrene can be used alone and / or in combination with methyl methacrylate as required. The one containing a part of the polymer in the methyl methacrylate monomer (that is, syrup) may be obtained by dissolving the polymer in the monomer, or by partially polymerizing the monomer. You may get it.

(Injection molding) The conductive resin composition of the present invention,
Alternatively, the method for producing a laminate can be applied to injection molding. When this injection molding is used, for example, a coating for forming the conductive resin composition is previously applied to the inner surface of the mold and dried or / and polymerized to form a film of the conductive resin composition. Then, the methyl methacrylate resin is melted and injection-molded to produce a laminate.

(Coating of Conductive Resin Composition) The thickness of the coating of the conductive resin composition formed on the inner surface of the above-mentioned molding die or casting polymerization mold is preferably 0.1 to 50 μm, It is particularly preferably 0.5 to 30 μm.
When the thickness of the coating exceeds 50 μm, the tendency of impairing transparency is intensified.

(In-Mold Molding) The laminate having the conductive resin composition obtained on the surface of the present invention can be further applied to in-mold molding. "In-mold molding" is edited by the Plastic Industry Research Group, "10th response to high functionality and high added value of surface decoration technology for exterior injection molded products-focusing on application examples" p.4-1 ~ 4-10 etc. refers to the molding method. In the case of using in-mold molding in this way, for example, after arranging a base material sheet having a coating film of the uncured product of the conductive resin composition on its surface so that the coating side faces the inner wall surface of the mold. By injecting a molten resin into a mold to cure the resin and then irradiating it with light, thereby curing the conductive resin composition layer on the surface to obtain a laminate having a conductive hard coat on the surface. be able to.

The laminated body in which the layer containing the conductive resin composition of the present invention is formed on the substrate is preferably 10 ⁸ Ω / □.
Below, the surface resistivity of 5 × 10 ⁷ Ω / □ or less is more preferable.

The surface of the laminate of the present invention has a pencil hardness of preferably 3H or more, more preferably 4H or more, and particularly preferably 5H or more.

[0086]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Parts means parts by weight (parts by weight) unless otherwise specified.

The coating film thickness, pencil hardness, coating adhesion and surface resistance in the examples and comparative examples were evaluated by the following methods.

(1) Coating film thickness: Using a microtome from the obtained laminate, a coating film made of a conductive resin composition was contained in a size of about 0.1 mm × 0.1 mm and a thickness of 100 n.
A transmission electron microscope (TEM:
It was observed by a photograph made by JEOL Ltd., model number JEM-100CXII.

(2) Pencil hardness: Measured according to JIS K5400 using a pencil scratch tester.

(3) Adhesion of coating film: According to JIS K5400. Vertical and horizontal 1 mm intervals on the surface of the test piece of the laminate
Make 100 cross-cuts by cutting one by one, attach a commercially available cellophane tape to the surface, and then remove the number (Y) of the squares left without peeling when rapidly peeling. It was displayed as Y / 100, and 100/100 was marked as good.

(4) Haze value: According to ASTM D1003, haze computer (manufactured by Suga Test Instruments Co., Ltd., model:
HGM-2DP).

(5) Surface resistivity: On the coating surface of a sample cut into a size of 45 mm × 45 mm, the probe was placed in the center of the square sample in parallel with one side, and manufactured by Mitsubishi Chemical Corp., Lorester. It was measured by a four-terminal method using a GP low resistivity meter.

In the following description, "part by mass" is abbreviated as "part".

Example 1

Pentaerythritol triacrylate ["Biscoat # 300", Osaka Organic Chemical Co., Ltd.] 4
To 8.7 parts, 88 parts of toluene, 88 parts of n-butanol,
Silicone-based surfactant (trade name: NUC
Silicone FZ-3789, Nippon Unicar Co., Ltd.) 1.3
Part, ITO ultra fine particles ["Pastran ITO-type
B ", manufactured by Mitsui Kinzoku Co., Ltd.] 50 parts, and a planetary ball mill type LP-4 (manufactured by Ito Manufacturing Co., Ltd.) with a diameter of 2.0 m
The zirconia crushing balls of m were used in an amount of 3 times the total mass of the mixture, and the zirconia crushing pot was used to perform dispersion for 5 hours under crushing conditions of 300 revolutions per minute.

To the mixture thus obtained, 107 parts of acrylic crosslinked resin fine particles [“MX-150”, manufactured by Soken Chemical Industry Co., Ltd.], 121 parts of toluene, 12 parts of n-butanol were added.
ULTRASONIC CLEANE manufactured by Inouchi Shigeido Co., Ltd.
RVS-150 was used to completely disperse the resin fine particles by ultrasonic irradiation for 3 hours under the conditions of an oscillation frequency of 50 Hz and an average output of 120 W. Further, a photoinitiator [“IRGACURE 184”, manufactured by Ciba-Geigy Co., Ltd.] was added to 4.9.
Then, ultrasonic irradiation was performed for 15 minutes under the above-mentioned apparatus and conditions.

This mixture was applied on a 30 cm × 30 cm general tempered glass plate for cell cast polymerization to a thickness of 30 μm using a bar coater of PI-1210 automatic coating device type 1 manufactured by Tester Sangyo Co., Ltd. For 5 minutes and at 80 ° C. for 10 minutes to give a coating thickness of 12 μm. Then, using a high-pressure mercury lamp with an output of 200 W, the coating is polymerized and cured by irradiation with ultraviolet rays three times under the conditions of an irradiation distance of 220 mm and a light amount of 600 mJ / cm ² per time, and a conductive resin composition having a thickness of 12 μm An object layer was formed.

The glass plate thus obtained and another glass plate for cell-cast polymerization (the same as the above glass plate for cell-cast polymerization) in which the conductive resin composition layer was not formed on the surface of the glass plate. Then, it was fixed with metal fittings in combination with a gasket made of soft vinyl chloride, and a casting polymerization mold for cell cast polymerization was assembled.

Polymerization containing 0.05 part by mass of a polymerization initiator, azobisisobutyronitrile, per 100 parts by mass of a syrup containing 30% by mass of polymethylmethacrylate and 70% by mass of methylmethacrylate in this casting polymerization type. The raw material was injected and polymerized in a hot water bath at 80 ° C. for 1 hour and in an oven at 130 ° C. for 1 hour. By decomposing the casting mold, a laminate having a thickness of 3 mm to which a conductive hard coat film made of a conductive resin composition was transferred was obtained. Table 1 shows the physical properties of the obtained laminate.

An electron microscope (TEM) photograph of this laminate is shown in FIG. In FIG. 1, the ITO ultrafine particles are shown as black dots. It will be understood from FIG. 1 that the ITO ultrafine particles form a mesh-shaped conductive path.

Example 2

Other conditions were the same as in Example 1 except that the thickness of the conductive resin composition layer was reduced to 5 μm.
According to the above, a laminate having the conductive hard coat film transferred thereon was prepared, and the physical properties of the laminate were measured.

Table 1 shows the physical properties of the obtained laminate.

Example 3 Continuous cast polymerization was carried out using the continuous polymerization apparatus shown in FIG. That is, the figure shows the mirror-finished coating film-forming coating material of the conductive resin composition used in Example 1 with stainless steel endless belts 1 and 2 having a thickness of 1.5 mm and a width of 3000 mm (length 200 m). In front of the syrup injection part 15 of the continuous polymerization apparatus shown in 3, the endless belt 2 is coated with a gauze type 1 manufactured by Daiwa Factory Co., Ltd., and the film thickness of the coating film is adjusted by a film thickness adjusting roll 18. Then, it was dried at 80 ° C. for 5 minutes in the drying zone to give a coating thickness of 12 μm on the endless belt 2.

Next, using three high-pressure mercury lamps 17 each having an output of 200 W, an irradiation distance of 220 mm and a light amount of 180 when passing.
The coating was irradiated with ultraviolet rays by passing it under a high pressure mercury lamp under the condition of 0 mJ / cm ² to polymerize and cure the coating to form a conductive resin composition layer having a thickness of 12 μm on the stainless steel belt 2. .

Then, the same syrup as that used in Example 1 was injected into the continuous polymerization device from the injection device 14. In this continuous polymerization apparatus, the distance between the belts 1 and 2 was adjusted to 4.2 mm by the syrup injecting section 14.

Under the condition that the residence time of the syrup in the first polymerization zone 8 is 35 minutes, 78
The syrup was polymerized while applying warm water of ℃.
In the second polymerization zone 10, the polymerization was completed by the far-infrared heater under the condition that the back surface temperature of the belts 1 and 2 was 120 ° C. so that the residence time of the syrup was 5 minutes.

Thus, a methacrylate resin plate having a plate thickness of 3 mm and having the conductive resin composition layer transferred to the surface was obtained. Table 1 shows the physical properties of the obtained resin plate.

This laminated body was examined with an electron microscope (TEM; 10,
000 times), it was found that ITO was the same as in FIG. 1 above.
The ultrafine particles formed a mesh-shaped conductive path.

Example 4 The conductive coating film-forming coating material used in Example 1 was a methyl methacrylate resin plate (Acrylite-L # 001, thickness 3).
mm, manufactured by Mitsubishi Rayon Co., Ltd.) by the same method as in Example 1 so that the film thickness after drying is 12 μm, and dried and polymerized and cured by the same method as in Example 1 to make the surface conductive. A methacrylic resin plate having a hard coat was obtained. The characteristics of the obtained resin plate were evaluated, and the results are shown in Table 1.

Example 5 A laminate having a conductive hard coat film on the surface was prepared in the same manner as in Example 4 except that the thickness of the conductive resin composition layer was reduced to 5 μm in Example 4. Then, the physical properties of the laminate were measured. The results obtained are shown in Table 1.

Comparative Example 1

Except that the acrylic crosslinked resin fine particles [“MX-150”, manufactured by Soken Chemical Industry Co., Ltd.] were not added in Example 1 and the thickness of the conductive resin composition layer was reduced to 5 μm. Other conditions were the same as in Example 1 to prepare a laminated body to which the conductive hard coat film was transferred. The physical properties of the obtained laminate are shown in Table 1.

An electron microscope (TEM) photograph of this laminate is shown in FIG. From this TEM photograph, it will be understood that the ITO ultrafine particles are uniformly dispersed in the coating film.

[0115]

[Table 1]

[0116]

EFFECT OF THE INVENTION The conductive resin composition of the present invention having the above structure gives a laminate having a conductivity of 10 ⁸ Ω / □ or less, even when a small amount of conductive particles is used. be able to.

The conductive resin composition of the present invention is particularly suitable for floor materials and wall materials in clean rooms, front plates of display devices,
Window glass, show window glass, instrument cover material,
Also, it can be suitably used as a packaging material for semiconductors.

[Brief description of drawings]

FIG. 1 is a TEM photograph of a cross section of a conductive coating film on the surface of the laminate obtained in Example 1.

FIG. 2 is a TEM photograph of a cross section of a conductive coating film on the surface of the laminate obtained in Comparative Example 1.

FIG. 3 is a schematic cross-sectional view showing an example of an apparatus that can be suitably used for continuous cast polymerization in the present invention.

[Explanation of symbols]

1, 2 ... Endless belt 3, 4, 5, 6 ... Main pulley 7 ... Carrier roll 8 ... First polymerization zone 9. Hot water spray 10 ... Second polymerization zone 11 ... Cooling zone 12 ... Gasket 13 ... Plate-shaped polymer 14 ... Polymeric raw material injection device 15 ... Application position of composition for forming film of conductive resin composition 16 ... Drying zone 17 ... High pressure mercury lamp 18 ... Film thickness adjusting roll

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // B29K 33:04 B29K 33:04 B29L 7:00 B29L 7:00 F term (reference) 4F100 AA33 AG00 AK01B AK25 AK25A AL05B AT00A BA02 BA07 CA18 CA30B DE01B GB08 GB41 JB14B JG01B JG03 JK12B YY00B 4F204 AA43L AA44L AB01 AB16 AE03 AG01 AG03 AH33 AH48 AH73 EA03 EA04 EB02 EB13 EK04 EK05 EK18 4J002 BG071 BN002 CE002 CQ011 DA036 DA076 DA086 DA096 DA106 DA116 DB006 DB016 DE046 DE097 DE117 DE137 DE147 DF016 DJ017 FB076 FD112 FD116 FD150 FD200 GQ00

Claims (12)

[Claims] 1. A phase (A) containing no conductive particles (X).
And a phase (B) containing conductive particles (X), wherein the conductive particles () are added in a continuous phase of the phase (B) containing conductive particles (X). A conductive resin composition, wherein the phase (A) containing no X) forms a dispersed phase. 2. The conductive particles (X) have an average particle diameter of 200 n.
The conductive resin composition according to claim 1, which is an inorganic fine particle having a particle size of m or less. 3. A phase (A) containing no conductive particles (X).
Has a minimum diameter of 200 nm or more, and contains an organic substance and / or an inorganic substance, The conductive resin composition according to claim 1 or 2. 4. Conductive particles (X) in a conductive resin composition
The volume ratio of the phase (A) which does not contain is 30 volume% or more, The electroconductive resin composition in any one of Claims 1-3 characterized by the above-mentioned. 5. A phase (B) containing conductive particles (X).
Contains 7 to 40% by volume of the conductive particles (X), and the conductive resin composition according to claim 1. 6. A phase (B) containing conductive particles (X).
Contains the photocurable resin composition, The conductive resin composition in any one of Claims 1-5 characterized by the above-mentioned. 7. A laminate comprising a base material and a layer which is disposed on the base material and which contains the conductive resin composition according to any one of claims 1 to 6. 8. The surface resistivity of the conductive resin composition layer is 10
The laminated body according to claim 7, which has a resistance of ⁸ Ω / □ or less. 9. The laminate according to claim 7, wherein the surface of the conductive resin composition layer has a pencil hardness of 3H or more. 10. The laminate according to claim 7, wherein the base material has a methyl methacrylate unit as a main component. 11. A composition for forming a film of the conductive resin composition according to claim 1, which is applied to the surface of a molding die or a casting polymerization die, and dried or / and polymerized and cured. Next, the base material is molded, and the base material is molded.
11. The method for manufacturing a laminate according to any one of 10. 12. The method for molding a base material is cast polymerization, which comprises a pair of endless belts which are opposed to each other and run at a predetermined interval, and which are sandwiched between a pair of endless belts in the vicinity of both end portions thereof. In the state, in the space portion formed by the two gaskets running following the running of the endless belt, the polymerizable raw material is continuously supplied from one end side of the endless belt to polymerize the polymerizable raw material. The method for producing a laminated body according to claim 11, wherein the plate-shaped laminated body is taken out from the other end of the endless belt.