JPS62207353A - Antistatic composition - Google Patents

Abstract

PURPOSE:To obtain an antistatic compsn. which can form a transparent electrically conductive film having excellent electrical conductivity, transparency and durability, a high hardness and mar resistance, consisting of a specified copolymer and an actinic radiation-curable resin. CONSTITUTION:A compsn. consists mainly of a copolymer (A) obtd. by copolymerizing an ionic electrolytic monomer having an ethylenically unsaturated group with a monomer having an ethylenically unsaturated group and an actinic radiation-curable resin (B). As the ionic electrolytic monomer, cationic electrolytic monomers having a cationic electrolytic group as well as an ethylenically unsaturated group are preferred from the viewpoint of electrical conductivity and salts having a quaternary ammonium group are particularly preferred. The amount of said monomer accounts for 10-40wt% of the total amount of the monomers.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to antistatic compositions.

[Conventional technology]

With the development of the electronics industry in recent years, semiconductor devices have also rapidly advanced and the use of plastics has also progressed, but at the same time various problems such as destruction of semiconductor devices due to static electricity charging have been brought into closer focus than ever before, and various problems have arisen. Coated with antistatic agent.

Among these antistatic agents, coating type antistatic agents are generally those that use surfactants, or conductive paints containing carbon particles or metal particles, and A technology has been proposed to create emulsion paints by introducing molecular electrolytes into polymers (Special Publication No. 57).
-22041 publication). On the other hand, the applicant of the present application also proposed (1) an emulsion that forms a conductive film with excellent durability as an antistatic agent (Japanese Patent Laid-Open No. 59-219304).
Publication No.).

[Problem that the invention seeks to solve]

However, these antistatic agents and low resistance processing agents
It has drawbacks such as lack of durability and formation of a black or opaque paint film.

That is, the above-mentioned surfactant (1) forms a conductive monomolecular film when applied, but it evaporates during long-term use, easily detaches from friction, and is further washed out by water or solvents.
It has the disadvantage that its conductivity decreases or disappears. In addition, the above-mentioned conductive paint is a composite material in which carbon-based particles and metal-based particles are mixed into a polymer, and although it is relatively durable, it lacks transparency and does not have a see-through function. However, it has drawbacks such as spoiling the appearance of the coated material and being unable to print. Furthermore, in the prior art (2), the obtained coating film (film) has improved transparency and is recognized to be more durable than the prior art (2), but it is still insufficient and difficult to put into practical use. It is something.

Further, although the emulsion (1) previously proposed by the applicant of the present invention forms a durable transparent conductive film, the hardness of the coating film is rather low, and the scratch resistance may be poor.

The present invention was made against the background of the above-mentioned conventional technical problems, and has excellent conductivity, transparency, durability, and high hardness.
An object of the present invention is to provide an antistatic composition capable of forming a transparent conductive film with scratch resistance.

[Means for solving problems]

That is, the present invention provides a copolymer obtained by copolymerizing (a) an ionic electrolyte monomer having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group; The present invention provides an antistatic composition characterized by containing an energy ray curable resin as a main component.

The antistatic composition of the present invention achieves the above object by containing (a) a specific copolymer and (b) an active energy ray-curable resin.

Hereinafter, the present invention will be explained in detail in terms of constituent elements.

(a) Copolymer The (a) ionic electrolyte monomer having an ethylenically unsaturated group constituting the copolymer of the present invention refers to a monomer having both an anionic or cationic electrolyte group and an ethylenically unsaturated group. You can use either one.

Typical examples include sodium styrene sulfonate, methacryloyloxyethyltrimethylammonium chloride, 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, and sulfonic acid groups, quaternary ammonium groups,
All ethylenically unsaturated monomers with salts such as sulfonium groups, phosphonium groups can be used, but
From the viewpoint of conductivity, cationic electrolyte monomers having both a cationic electrolyte group and an ethylenically unsaturated group are preferably used, and in particular salts containing a quaternary ammonium group, such as methacryloyloxyethyltrimethylammonium chloride, 2-hydroxy -3-methacryloyloxypropyltrimethylammonium chloride is preferably used.

The ionic electrolyte monomer (a) having an ethylenically unsaturated group may be used alone or in combination with two
More than one species can also be used together.

The proportion of the ionic electrolyte monomer having an ethylenically unsaturated group in the total monomers is 10 to 40%,
Preferably 20-40% (by weight, (al+(b)
-100% by weight, the same applies hereinafter), and if it is less than 10% by weight, the desired conductivity cannot be fully exhibited, while if it is used in excess of 50% by weight, the conductivity will reach equilibrium, and the conductivity Furthermore, the molecular weight of the resulting copolymer may not be sufficiently large due to too large a proportion of the ionic electrolyte monomer containing an ethylenically unsaturated group.

The proportion of the ionic electrolyte monomer (a) having an ethylenically unsaturated group in the composition of the present invention is usually 5 to 18% by weight, preferably 7 to 15% by weight, If it is less than 5% by weight, the resulting composition will not have sufficient antistatic performance, while if it exceeds 18% by weight (
b) The proportion of the active energy ray-curable resin may decrease, and the hardness and scratch resistance of the coating film formed from the composition of the present invention may decrease.

In addition,...) Monomers having an ethylenically unsaturated group include, for example, vinyl acetate, styrene, alkyl acrylate, alkyl methacrylate, ethylene, propylene, vinyl chloride, acrylonitrile, ethylene glycol dimethacrylate, and trimethylol trimethacrylate. Propane, (meth)acrylic acid, itaconic acid, citra, conic acid,
Fumaric acid, maleic acid, N-methylol (meth)acrylamide, alkoxymethyl (meth)acrylamide,
Examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxybrobyl (meth)acrylate, dimethylamino-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, and (meth)acrylamide.

Such a monomer (b) having an ethylenically unsaturated group is
One type can be used alone or two or more types can be used in combination.

Further, the usage ratio of the monomer having an ethylenically unsaturated group (bl) to the total monomers is 50 to 90% by weight, preferably 60 to 80% by weight.

The copolymer (a) used in the composition of the present invention is:
It can be easily produced by radical emulsion polymerization of a mixture of the monomers (a) to (b) in an aqueous medium or by radical polymerization in an organic solvent. preferable.

Preferred organic solvents used in this case include alcohols such as methanol, ethanol, i-propyl alcohol, n-propyl alcohol, and i-butyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monoethyl ether. Polyhydric alcohol derivatives such as acetate and ethylene glycol monobutyl ether can be used; however, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; A mixed solvent containing esters such as isobutyl acetate, ethyl acetate, and butyl acetate may also be used.

Examples of initiators used in the copolymerization reaction include organic peroxides such as benzoyl peroxide, cumene hydroperoxide, lauroyl peroxide, and paramenthane hydroperoxide, and azo radical initiators such as azobisisobutyrinitrile. Ru. The amount of such a radical initiator used is usually 0.1 to 10 parts by weight or 0.5 to 10 parts by weight per 100 parts by weight of all monomers.
5 parts by weight. Further, in this radical copolymerization, xmm matching molecules such as dialkylxanthogen disulfide and t-dodecylmerbutane can also be used. (a) to (b) Monomers, radical initiators, etc.
It may be added in its entirety at the start of the polymerization, or it may be added in portions after the start of the polymerization, and the polymerization method may be a batch method or a continuous method.

Copolymerization is usually carried out in a nitrogen atmosphere or the like from which oxygen is removed, and the polymerization temperature is 50 to 100'p and the polymerization time is about 5 to 10 hours.

After the copolymerization reaction is completed, the obtained polymerization solution may be mixed with the active energy ray-curable resin described later to form the composition of the present invention, or it may be once poured into a non-solvent and precipitated. After collecting the copolymer, for example, the obtained copolymer and an active energy curable substance (to be described later) may be mixed using an organic solvent if necessary.

(b) Active energy ray curable resin Active energy ray curable resin is a composition consisting of a photosensitive compound and a polymer that is crosslinked and cured by irradiation with active energy rays such as ultraviolet rays, electron beams, and far ultraviolet rays. thing(
Hereinafter, known resins such as [hereinafter referred to as photosensitive compositions] or (2) crosslinked and hardened polymers (hereinafter referred to as "photosensitive polymers") can be mentioned.

Here, the above-mentioned photosensitive composition (1) is, for example, a composition in which a cyclized product of an isoprene polymer or a butadiene polymer is combined with a photosensitive compound such as a bisazide compound (for example, a p-quinone azide compound), or a composition in which a bisazide compound is combined with a polydiorganosiloxane. Examples include compositions in which compounds are combined.

In addition, (1) photosensitive polymers include epoxy acrylates such as epoxy acrylate made by reacting an epoxy resin with an acrylic acid and methyltetrahydrophthalic anhydride, and epoxy acrylate made by reacting an epoxy resin with 2-hydroxyacrylate; Unsaturated polyesters such as copolymerized esters of glycidyl acrylate and phthalic anhydride, esters of methacrylic acid dimer and polyol, and esters of polyethylene glycol, maleic anhydride, and glycidyl methacrylate; polyethylene glycol and 2.4- ) Urethane acrylates such as those obtained by reacting polyurethane synthesized from lylene diisocyanate with 2-hydroxyethyl methacrylate or N-methylol acrylamide, and those obtained by urethanizing hydroxyethylphthalyl methacrylate with xylene isocyanate; Polyvinyl alcohols containing unsaturated groups, such as those made by reacting polyvinyl alcohol with N-methylolacrylamide; those having carboxyl groups in the side chains, such as those made by reacting allylamine with an ethylene-maleic anhydride copolymer (
Poly(meth)acrylic acid or maleic acid copolymers made by introducing an unsaturated group into the carboxyl group in the polymer of meth)acrylic acid or maleic acid; Examples include silicone resins condensed with methoxysilane or monocinnamoyloxydimethyljethoxysilane.

These photosensitive compositions or photosensitive polymers may contain reactive diluents such as 2-ethylhexyl acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, jetoxyacetophenone, A photopolymerization initiator such as isobutyl benzoin ether, benzyl dimethyl ketal, benzophenone, etc. may be blended.

These (b) active energy ray-curable resins include:
Particularly preferred are epoxy acrylates and/or urethane acrylates.

These (1) photosensitive compositions or (1) photosensitive polymers are 1
A single species can be used alone, or two or more species can be used in combination.

In the composition of the present invention, the ratio of (a) copolymer and (b) active energy ray-curable resin is 1 in terms of solid content weight ratio.
:l to 1:3, preferably 1:1.5 to 1:2.5; (i) If the copolymer is too small, the conductivity of the resulting composition will decrease, while if it is too large, the resulting composition will have poor conductivity. When a coating film is formed using the composition, the hardness decreases and the scratch resistance becomes poor.

The composition of the present invention is prepared by combining the above-mentioned (a) copolymer and (b) active energy curable resin in an organic solvent, such as the organic solvent used as the polymerization solvent, and usually at a solid content concentration of 10. The content is adjusted to 90% by weight, preferably 30 to 50% by weight.

Incidentally, an organic polar solvent can also be added to the organic solvent in order to improve the adhesion to the material to be coated. This organic polar solvent is an organic solvent that has polarity in its molecules,
For example, picoline, monoethanolamine, jetanolamine, morpholine, dimethylformamide, dimethylacetamide, hexamethylphosphortriamide, N-
Examples include nitrogen-containing compounds such as methylpyrrolidone; sulfur compounds such as sulfolane and dimethylsulfoxide.

These organic polar solvents can be used alone or
Alternatively, two or more types can also be used in combination. In particular, dimethylformamide (DMF) and/or dimethyl sulfoxide (DMSO) are preferred as the organic polar solvent.

In general, plastics that require coating with antistatic compositions include polyvinyl chloride, polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, and solvents that attack these plastics include ketones and aromatic compounds. There are many hydrocarbons, cellosolves, etc., but even if these organic solvents are used, it may not be possible to improve the adhesion of the resulting antistatic composition to the material to be coated. By adding a solvent,
It becomes possible to improve adhesion.

The amount of organic polar solvent added is usually 100 parts by weight of the composition (
The organic polar solvent is used in an amount of 1 to 40 parts by weight, preferably 5 to 30 parts by weight, based on solid content (in terms of solid content). On the other hand, if the amount exceeds 40 parts by weight, the adhesion improves, but the antistatic properties, durability, etc. that the composition originally has may deteriorate.

Furthermore, the composition of the present invention comprises the above-mentioned (a) copolymer and (b)
Although the active energy ray-curable resin is the main component, appropriate amounts of ordinary coating resins, preservatives, pigments, plasticizers, and surfactants may also be blended.

The antistatic composition of the present invention has excellent antistatic properties, durability, transparency, and adhesion, and has high hardness and scratch resistance. It can be effectively used in applications such as inhibitors and paints.

[Effect]

In the antistatic composition of the present invention, the copolymer (a) imparts conductivity, and (b) imparts hardness and scratch resistance to the coating film from which the active energy ray-curable resin is obtained. ,
This makes it possible to form a coating film that has good conductivity, is hard, and has scratch resistance.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples. In the examples, parts and percentages are based on weight unless otherwise specified.

Reference Example 1 405 parts of methyl cellosolve, 194 parts of methanol, 80 parts of methacryloyloxyethyltrimethylammonium chloride, 60 parts of styrene, and 30 parts of methyl methacrylate were placed in a polymerization tank equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen introduction tube. , butyl acrylate, 10 parts of acrylic acid, and 1 part of benzoyl peroxide were supplied, and the mixture was stirred and heated while introducing nitrogen to carry out a polymerization reaction at 80° C. for 5 hours. The obtained antistatic copolymer solution A had a solid content concentration of 251% and a viscosity of 150 c.
ps/25°C.

Examples 1 to 3 and Comparative Examples 1 to 3 Urethane acrylate (manufactured by Dainippon Ink & Chemicals 01, ultraviolet curable paint, Unidic 17-824, solid content Concentration 7
5%) were mixed at the solid content ratio (weight ratio) shown in Table 1 to obtain a composition having ultraviolet curable and antistatic properties.

Table 1 Each of the above compositions was coated on a polyester film with a thickness of 1008 m using a bar coater #10, and heated at 60°C.
After pre-drying for 5 minutes at
The sample was irradiated with ultraviolet light for 30 seconds using a high-pressure mercury lamp (15 cm). The results of the coating films obtained are shown in Table 2.

(Margin below) Table 2 In Table 2, each evaluation item is as follows.

■Transparency: Visually compared with a 100 μm thick polyester film as a base material.

■Surface resistance value; Manufactured by Tokyo Electronics ■, STACK
Measured using TR-3. Note that the surface resistance value was measured under the same conditions (25° C., 50% RH) after being left in a sealed container with adjusted humidity for 1 hour or more.

■Pencil hardness; Measured in accordance with JIS K-5400 standard.

■Adhesion: Based on cellophane tape peel test.

The evaluation of transparency and adhesion was based on ◯: good, △: slightly poor, ×: poor.

As is clear from the results in Table 2, the conductive film formed from the composition of the present invention has excellent transparency, hardness, adhesion, and durability.

〔Effect of the invention〕

The coating film formed from the antistatic composition of the present invention is
It is composed of a copolymer in which a conductivity-imparting material is copolymerized into the polymer molecular chain and an active energy ray-curable resin, so it cures quickly and efficiently when exposed to active energy rays such as ultraviolet rays, and has strong conductivity. It can form a polymer film with excellent transparency, hardness, scratch resistance, adhesion, and durability, and is particularly useful as an antistatic coating.

Patent applicant: Achilles Corporation Agent: Patent Attorney Takashi Shirai 6. Contents of amendment Voluntary writing of procedural amendments) January 22, 1986

Claims (1)

[Claims] (1) (a) A copolymer obtained by copolymerizing (a) an ionic electrolyte monomer having an ethylenically unsaturated group and (b) a monomer having an ethylenically unsaturated group, and (b) active energy rays. An antistatic composition whose main component is a curable resin.