TW200302258A - Coating composition and antistatic hard-coated film - Google Patents

Abstract

The object of the present invention is to provide a coating composition which can continuously and evenly form a hard coat layer excellent in antistatic property, transparency, wear resistance, and chemical resistance and an antistatic hard-coated film having a hard coat layer formed by applying the composition. The coating composition comprises an ultraviolet- or radiation-curable resin which has at least three methacrylic groups and cures upon irradiation with ultraviolet or a radiation, a conductive polymer, and a compatibilizing agent having one or two methacrylic groups and at least one hydroxy group; provided that when the ultraviolet- or radiation-curable resin has a hydroxy group in the molecule, then the composition need not contain the compatibilizing agent; an antistatic hard-coated film having a hard coat layer formed by applying the composition is provided.

Description

200302258 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a coating composition for forming a conductive hard coat layer, and an antistatic charge formed by coating and curing the composition on a thermoplastic resin film. The hard coating film is, in detail, an anti-charge hard coating film for protecting the surface of an electronic information display suitable for screen display of a television photoelectric receiver and a personal computer. [Prior art] Various display objects or glass, such as liquid crystal displays, CR, plasma displays, outdoor display boards, photoelectric display panels, etc., are protected by a thermoplastic resin film with a hard-coating treatment on the surface. The thermoplastic resin film has high volume intrinsic resistance, so it is easy to be charged with static electricity by rubbing on the contact surface, and it will not leak out. Therefore, the static electricity itself or the adsorption of dust due to the static electricity may reduce the productivity in the assembling step of the display object. Further, when it is actually used as a display, the visibility is significantly reduced due to the adsorption of dust on the surface, which is a problem. In order to improve these problems, a surfactant is used as a conductive agent in a thermoplastic resin, or it is added to a coating material and applied to the surface of a thermoplastic resin film or a molded article to improve conductivity and prevent charging. In the case of blending a surfactant with a thermoplastic resin, generally, the thermoplastic resin has low polarity and poor compatibility with highly polar surfactants, or because the molecular weight of the surfactant is small, it passes the interface activity over time. The agent will bleed to the surface of the thermoplastic resin, causing surface tackiness, and at the same time, it will cause a decrease in transparency and prevent a decrease in electrification. The effect is 6 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258 Low continuity is the problem. In addition, when a surfactant and a hard coat agent are applied together as a coating on the surface of a film, a low-molecular-weight surfactant may cause stickiness on the surface, or may pass over time due to the effects of temperature, humidity, and light. There is a problem that the antistatic effect is reduced, and the weather resistance or the durability of the antistatic effect is deteriorated. In order to prevent performance degradation due to bleeding or surface mobility, high molecular weight conductive polymers have been put to practical use. Conductive polymers have conductive units in the molecule. The conductive polymer unit is a highly polar hydrophilic group such as an ionic group or a low-molecular-weight ether bonded to a polymer to impart conductivity. However, if a high-polarity conductive polymer is blended into a thermoplastic resin, the compatibility with the low-polarity thermoplastic resin will be deteriorated, resulting in uneven appearance and uneven appearance due to non-uniform dispersion of the conductive polymer. Decreased transparency (turbidity), and the hardness of conductive polymers and thermoplastic resins are not sufficient, especially when it is intended to protect the surface of electronic information displays, which has serious problems. In addition, when a conductive polymer and a hard coat agent are applied as a coating on the surface of a film, although problems caused by bleedout do not occur, agglomeration of the conductive polymer often occurs, resulting in the formation of agglomerates. Uneven appearance and reduced transparency (turbidity). Especially for the film used to protect the surface of the electronic information display, in addition to the conductivity and the durability of its effect and the hard-coating property, the non-coloring property of the film and the transparency without fogging are important requirements. Transparent hard-coating film, transparent hard-coating film, 7 312 / Invention Manual (Supplement) / 92-03 / 91137460 200302258 Outer line or radiation-hardening resin of the parent company density bureau, this hardening type The “resin” is obtained by applying a coating composition containing a monomer or oligomer polymerized and hardened by irradiation with ultraviolet rays or radiation as a main component through irradiation with ultraviolet rays or radiation. In this coating, a conductive polymer is mixed and dissolved, and the coating is applied on the surface. 'As the solvent volatilizes, the aggregation of the conductive polymer is often prone to occur.' Haze caused by the aggregate of the conductive polymer is generated. ), As a result, there is a problem that the transparency, the uniformity of appearance, and the visibility are reduced. The use of such a conductive polymer does not require improvement. As a technique other than the use of a conductive polymer to improve the problem of using a surfactant as a conductive agent, a person skilled in the art has the following technique. For example, 'Yukkai Hei 6-2 6 3 9 0 3 discloses that in order to reduce the temperature dependency of the conductivity of the resin plate and to improve the durability of the transparency of the film, the use of antimony-doped Metal oxide ultrafine particle coating technology is applied to the surface of a resin plate to harden it. In addition, Japanese Patent Application Laid-Open No. 6-8 7 9 6 5 discloses the purpose of forming a surface of a synthetic resin molded product such as an optical disc or a video tape with excellent transparency, excellent conductivity, and durability. A technique of photopolymerizing and curing a monofunctional (meth) acrylfluorenyl compound having a quaternary ammonium salt of a sulfonic acid group together with a crosslinkable oligomer. In addition, Japanese Patent Application Laid-Open No. 20 QQ-2 8 2 0 1 4 discloses that in order to form a light-hardening type anti-charge hard coating film on the plastic surfaces of automobile parts, organic thin film glass, signboards, etc., A mixture of a hydrolyzate of a silane compound containing a grade 4 ammonium structure and (meth) acrylic acid 醯 8 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258 A hydrolyzate of a hydrolyzable functional silane and a polyfunctional (methyl) Acrylate polymer hardens together. [Summary of the Invention] (Problems to be Solved by the Invention) However, the above-mentioned known technologies have the following problems, respectively: In the technology of JP-A-6-263-6903, the coating formed by the coating The metal oxide ultrafine particles are colored due to absorption in the visible light region, and the transparency at a specific wavelength is greatly reduced, which is not suitable for the surface of an electronic information display such as a CRT. The technique of JP-A No. 6-8 7 9 6 5 can ensure the electric conductivity with a small amount of use, but the hard-coating property is not sufficient. If the hard-coating property is to be ensured, the electric conductivity is insufficient. . The technique of JP 2 0 ◦ 0-2 8 2 0 1 4 requires a long time in order to use a special silane compound and obtain a hydrolyzate thereof. In industrial practice, the steps are complicated, the productivity is poor, and the silane The problem is that compounds have poor resistance to basic drugs. As described above, in an electronic information display, it is very difficult to obtain a sufficiently hard-preventing hard-coating film. Therefore, an object of the present invention is to provide a coating composition that is not only excellent in chargeability, transparency, abrasion resistance, and chemical resistance, but also can continuously and uniformly form a non-colored and mist-free hard coating layer. And an anti-charge hard coating film having a hard coating formed by applying the composition and hardened by ultraviolet or radiation. (Means to Solve the Problem) 9 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258 The present inventors, etc., have tried to reduce the polymerization that is the cause of the above-mentioned problems in terms of ease of use of conductive polymers. The agglutination of the material was investigated. As a result, it was found that as a component of a monomer or oligomer that is hardened by osmium external radiation or radiation polymerization to form a hard-coat resin film, it was made to have at least one (meth) acrylic fluorene group and at least one hydrogen The above-mentioned problem can be solved by using an oxygen-based compound (that is, a compatibilizing agent) as an essential component. The present invention has been completed. That is, the present invention is a coating composition comprising at least three

(Meth) acrylfluorene-based ultraviolet or radiation hardening resin, conductive polyσ, and a compatibilizing agent having one or two (meth) acrylfluorene groups and at least one hydroxyl group, the The ultraviolet- or radiation-curable resin may not contain the compatibilizer when it contains a hydroxyl group in its molecule. As used herein, the term "(meth) propanefluorenyl" refers to both acrylfluorenyl and methacrylfluorenyl. Also, the "ultraviolet or radiation-curable resin" is a monomer / copolymer used for forming a hard coat layer by irradiation with ultraviolet rays or radiation. It may contain a hydroxyl group. In the case where the coating composition has a hydroxyl group in the molecule of the ultraviolet- or radiation-curable resin, since the ultraviolet- or radiation-curable resin has the function of a compatibilizing agent, it may not contain a compatibilizing agent. That is, the equivalent of this ultraviolet- or radiation-curable resin-based compatibility agent. X. This coating composition 'may contain such a compatibilizer even if it has a hydroxyl group in the molecule of ultraviolet or radiation curable resin. The feature of this invention is the formula, which uses a compound having a hydroxyl group & (meth) propanyl as an essential component. We believe that this compound can function as a compatibilizer for ultraviolet or radiation curable resins and conductive polymers 312 / Invention Specification (Supplement) / 92-03 / 91137460 10 200302258. Thereby, the agglomeration property of the conductive polymer can be improved, and an antistatic hard coat film having uniformity and excellent visibility without fogging (cloudiness) or coloration can be obtained. However, when the ultraviolet or radiation curable resin itself has a hydroxyl group, although it can achieve the purpose by itself, it is also possible to use ultraviolet or radiation curable resin with this compound (that is, a miscibility agent) to further improve the conductivity. Of agglomerated polymers. In addition, the conductive polymer in the coating composition is substantially any of polyether, a polymer containing a level 4 ammonium salt group, a polymer containing a sulfonic acid, or a polymer of a charge-shifting polymer of a polymer. One. The conductive polymer is preferably a polymer containing a level 4 ammonium salt group, and more preferably a (meth) acrylate copolymer containing a level 4 ammonium salt group. Polymers containing a level 4 ammonium salt are readily available and have good electrical conductivity. The molecular weight of the conductive polymer in the coating composition is preferably 2 X 104 to 50 X 104. If the molecular weight is smaller than this range, there is a high risk of exudation at a high temperature. If the molecular weight is larger than this range, a large amount of the compound needs to be used in order to obtain the necessary conductivity, and therefore the hardness of the film is relatively reduced. The proportion of the conductive polymer to the solid matter at the time of hardening of the coating composition is preferably from 10 to 4% by weight. As ultraviolet or radiation curable resins, oligomers are usually used. If the ultraviolet- or radiation-curable resin is an oligomer, the reaction is fast, and it can impart a certain degree of flexibility to the formed film, and can prevent the adhesiveness to the carrier and cracking of the film. However, in the present invention, the use of an oligomer is not necessary, and we believe that a conductive polymer can take its place. 11 312 / Description of the Invention (Supplement) / 92-03 / 91137460 200302258 The compatibilizing agent is preferably a monomer polymerized or hardened by ultraviolet or radiation or an oligomer having a molecular weight of 1 X 1 Q 3 or less. This monomer or oligomer may be the same as or different from the ultraviolet or radiation curable resin used in the coating composition. The proportion of the compatibilizing agent or its equivalent with respect to the solid matter at the time of curing of the coating composition is preferably 5% by weight or more. This equivalent refers to an ultraviolet- or radiation-curable resin having a hydroxyl group in the molecule. The necessary amount of the compatibilizing agent or its equivalent varies depending on the type of the ultraviolet or radiation-curable resin or conductive polymer used, and it is not necessary to be constant. When the content is more than 5% by weight, aggregation is extremely small, and when the content is less than 5% by weight, the aggregation becomes significant in many cases. In order to improve the cohesiveness of the conductive polymer to form a uniform and well-recognizable film, it is generally appropriate to make the film solid matter 20% by weight or less. The present invention is also an anti-charge hard coating film, which has a coating composition coated on at least one side of a thermoplastic resin film with the coating composition of any of the above and is hardened by irradiation with ultraviolet rays or radiation to form electrical conduction Hard coating. The so-called ultraviolet light refers to electricity fei with a wavelength in the range of 1 to 390 nm; the wave "so stomach radiation" refers to three kinds of alpha rays, dotted lines, that is, 7 lines, and particle induction with the same degree of energy. Radioactive or cosmic rays. This anti-charge hard coating film is colorless, transparent, and non-fogging. It is suitable for protectors of electronic information display surfaces such as c R τ and liquid crystal displays. Furthermore, because it can withstand harsh environments, it is also It can be used as a protective film for information displays under harsh environmental conditions such as cabins, places for storing chemicals, outdoor cars in summer, etc. 12 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258. The plastic resin film is preferably triethylfluorene-based cellulose. Among the thermoplastic resin films, especially the triethylfluorene-based cellulose film can exhibit the effects of the present invention most prominently. [Embodiment] Hereinafter, an ultraviolet or radiation curable resin is referred to as a "curable resin". The hardening resin used in the present invention is not particularly limited as long as it is a resin having at least three (meth) acrylfluorene groups and hardened by ultraviolet rays or radiation, and may be appropriately obtained from an acrylic resin (including methacrylic acid). Resin), urethane acrylate, polyester acrylate and epoxy acrylate. The hardening resin used in the present invention may be one kind or a mixture of two or more kinds. In addition, in the case of two or more kinds, it may be one having a hydroxyl group and one having no hydroxyl group. mixture. As a typical example, the following can be exemplified. However, in addition, books published in general (such as UV · EB Handbook (raw materials), 1985, Polymer Journal (shares), photosensitive material List_up, 1996, text extended edition ) Can also be used. The following compounds are called (meth) acrylates. It contains both acrylate and methacrylate, and the structural formula is expressed by acrylate. (a) Trimethylolpropane tri (meth) acrylate (as shown below) CH2OCOCH = CH2 CH3CH2-C-CH2 OCOCH = ch2 ch2ococh = ch2 13 312 / Invention Specification (Supplement) / 92-03 / 9113 7460 200302258 (b) Trimethylolpropane tetra (meth) acrylate (as shown below)

Ol2〇COCH = CH2 CH2OCOCH = CH2

C2H5—C— CH2OCH2—C—CjHs »I ch2ococh = ch2 ch2cx: och = ch2 (c) Pentaerythritol tetra (meth) acrylate (as shown below) ch2ococh = ch2 CH2 = CHCOOCHz-C-CH2OCOCH = ch2 ch2ococh = ch2 ( d) Dipentaerythritol hexa (meth) acrylate (as shown below) CH2〇COCH = CH2 CH2 = CHCOOCH2-C-CH2〇CH2-c-ch2ococh-ch2 CH2OCOCH = CH2 ch2ococh = ch2 (e) tri (methyl) propane CH2 = CHCOOCH2CH2〇x CH2 = CHCOOCH2CH2O-P = ο CH2 = CHCOOCHjCHzO7 (f) Pentaerythritol tri (meth) acrylate (as shown below) ch2ococh = ch2 hoch2- c a ch2ococh = ch2 CH2OCOCH = CH2 (g) dipentaerythritol monohydroxypenta (meth) acrylate (as shown below)

CH2〇COCH = CH2 CH2〇COCH = CH2 CH2 = CHC00CH2 ~ C-CH20CH2 --C-CH2OH ch2ococh = ch2 ch2〇coch = ch2 312 / Specification of the Invention (Supplement) / 92-03 / 91137460 200302258 (h) Two ( (Methyl) Epichlorohydrin Modified Glyceryl Propionate (as shown below)

CH2〇CH2CHCH2〇COCH = CH2 OH

CH OCH2CH CH20 COCH = CH2 I OH CH2OCH2CHCH2OCOCH = CH2

I

OH (i) tri (meth) acrylic epichlorohydrin modified trimethylolpropane (as shown below)

OH

I CH2OCH2CH-CH2OCOCH = CH2 CH3CH2 ~ C-CHz〇CH2CHCH2OCOCH = ch2

I OH CH2OCH2CHCH2OCOCH = ch2

OH as the isocyanate series are: (j) ginseng (propenyloxyethyl) isocyanate (the following formula) 0

II CH J = CHCOOCHaCHi ^ N n ^ CH2CH2〇COCH = CH2 〇 ^ CxsN / C ^ 0 CH2CH2〇COCH = CH2 Examples: Polyesters and polybasic acids and / or their anhydrides and (meth) acrylic acid esters Polyester (meth) propionate obtained by chemical conversion; polyurethane (meth) acrylic acid obtained by reacting a polyol, a polyisocyanate, and a (meth) acrylate containing a hydroxyl group vinegar. 15 312 / Description of the Invention (Supplement) / 92-03 / 91137460 200302258 Among the above-mentioned hardening resins having 3 or more (meth) acrylfluorenyl groups, it is necessary to use them when using compounds without a hydroxyl group. A compound having a hydroxyl group and a (meth) acrylfluorenyl group as shown below. In the case where the hardening resin has three or more (meth) acrylfluorene groups and further has a hydroxyl group, these compounds and a conductive polymer can be used as a coating material. Even in this case, if a compatibilizing agent is used, the compatibility is considered in terms of compatibility, which is beneficial to the stabilization of the coating material and prevents the aggregation of the conductive polymer. Since any of these compounds can react to form a three-dimensional structure through irradiation with ultraviolet rays or radiation, it can be used as a structural component of a hard coat film. Therefore, the amount used is preferably 50 to 80% by weight as a solid matter when the coating composition is hardened. A photopolymerization initiator (hereinafter referred to as an "initiator") is necessary when the curing reaction is performed with ultraviolet rays. A benzophenone-based initiator, a diketone-based initiator, an acetophenone-based initiator, or a benzoin-based initiator may be used. Any of the well-known initiators, such as an initiator, a dibenzothiopiran-based initiator, and a quinone-based initiator. Generally, the initiator is used in an amount of 1 to 1% by weight based on the hardening resin. On the other hand, when a hardening reaction is performed via radiation, an initiator is not necessary. The conductive polymer used in the present invention can be used for the purpose of imparting antistatic properties to a hard coat layer, and examples thereof include the following compounds: As the polyether, polyolefin oxide, polyetheresteramide, Olefins-epoxychloropropane copolymers, methoxypolyalkylene glucosyl (meth) acrylate copolymers, etc., as olefins containing ethylene, propylene, or the like 16 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258 Both parties are better. As the polymer containing a level 4 ammonium salt group, as the polymer containing a level 4 ammonium salt group, any polymer may be used as long as it is a polymer containing a level 4 ammonium salt group (preferably containing a level 4 ammonium salt). The fourth-order ammonium salt is a salt of the fourth-order ammonium with an acid or a halogen. The acid is mainly an acid such as sulfonic acid or hydrochloric acid. Regarding polymers containing a level 4 ammonium salt, the representative structural formulas (wherein, m and η each represent an appropriate integer) are exemplified as follows: (1) (Methyl) containing a level 4 ammonium salt Acrylate copolymer (a part of a polymer composed of styrene, acrylonitrile, butadiene, vinyl chloride, and mixtures thereof is copolymerized with (meth) acrylate having a level 4 ammonium salt and The compound formed)

(2) Part of a polymer of cis-butadiene-embedded imine containing a 4th ammonium salt group (in a polymer composed of styrene, acrylonitrile, butadiene, vinyl chloride, and mixtures thereof) Compounds copolymerized with butadiene dieneimine having a 4th level ammonium salt group) 312 / Inventory (Supplement) / 92-03 / 91137460 (CH-OH) m (CH2 " CH2) j

17 200302258 (3) One portion of methacrylic acid imide copolymer containing quaternary ammonium salt (in θ 13 acid ester, methacrylate, and methacrylic acid imine copolymer)棊 compounds) ch3 (CH2-C) | — C00CH3 (CH'j ^ H2

CHrCH2- CH3 (4) Carbobetaine graft copolymer containing 4 grade money base (compound formed by grafting of carbobetaine grade 4 ammonium salt with polyethylene or polypropylene) • (CH2-CH2) i (CH-C〇.CH2 ^ II ο δδ〇0 H2-N ^ H2-COO) hr- ^ CH, ch2cock As a sulfonic acid-containing polymer, containing sulfonic acid or sulfonate The polymer is preferably in the form of, for example, sodium polystyrene sulfonate, or a copolymer thereof with acrylonitrile, butadiene, and a mixture thereof. Among these conductive polymers, polyether, a polymer containing a level 4 ammonium group, and a polymer containing a sulfonic acid are preferred, and 312 / Invention Specification (Supplement) containing a level 4 ammonium group / 92-03 / 91137460 18 200302258 Polymers are better, of which (meth) acrylate copolymers containing a level 4 ammonium salt group are highly conductive, and there are a variety of commercially available products, as well as the types of base polymers. There are many, it is easy to select the one with high affinity with the hardening resin, so it is particularly good. The average weight molecular weight of the conductive polymer is preferably 2X104 ~ 50X104, and 2X104, which is determined by polystyrene as a standard by GPC (GEL PERMEATION CHROMATOGRAPHY). 4 ~ 3 0 X 1 0 4 is more preferable. When the molecular weight is too small, the film forming property is low and blocking is likely to occur (b 1 0cki ng). When the molecular weight is too large, the compatibility with the hardening resin is poor, and it will become a non-uniform coating, and it will disperse in the solvent. During the process, many agglomerates are produced. The content of the conductive polymer is preferably 10 to 40% by weight with respect to the solid matter at the time of hardening of the coating material for the hard coat layer. If the content of the conductive polymer is too small, it may not be sufficiently caused. The adsorption of water molecules on the surface makes it impossible to exert the charging prevention performance. On the other hand, if the content is too large, the ratio of the relatively hardening resin will decrease, and the hard coat property (scratch resistance) will be significantly reduced. In addition, by using an amount in this range, moderate softness and impact resistance can be imparted to the hard coat layer, and adhesion can be improved. Hardened resins and conductive polymers have poor polarities as described above, so they are poorly compatible as described above, and they are used together with solvents to make coatings. During the drying process of coating onto films, the conductive polymers will aggregate to form agglomerates. Thing. As a function of preventing the aggregation of conductive polymers and imparting an affinity to the hardening resin, a miscible agent having a hydroxyl group and a (meth) acryl group may be used. Thing. 19 312 / Explanation of the invention (Supplement) / 92-03 / 91137460 200302258 The miscibility agent having such an effect can be exemplified as follows: (a) A compound having one hydroxyl group and one (meth) acryl group : (Meth) acrylic acid 2-via ethyl acetate (ch2 = chc00ch2ch2h0), (meth) propionic acid 2-hydroxypropionamine (ch2 = chc00ch2ch0hch3), (methyl) 4-Hydroxybutyl acrylate (ch2 = chc〇ch2ch2ch2ch2〇h), (meth) propionic acid 2-hydroxy-3 _phenoloxypropyl ester (as shown below) ch2 = chco och2chch2o- ^

OH (meth) acrylic acid modified ethylene phthalate (as shown below) j ^ N ^ COOCii2CH2OH k ^ COOCH2CH2OCOCH = CH2 (meth) acrylic polypropylene glycol (ch2 = chc〇 (〇ch2chch3) 12 〇Η) ; (B) a compound having one hydroxyl group and two (meth) acrylfluorenyl groups: di (meth) acrylic acid and glyceryl di (meth) acrylate (CH2 = CHCOOCH2CHOHCH2OCO ch = ch2), di (meth) acrylic acid ring Oxyethylene modified phosphate (as shown below) 0

CH2 = CHC00CH2CH20 \ II

/ P-OH CH2 = CHC00CH2CH20〆 (c) A compound having 2 hydroxyl groups and 1 (meth) acrylic acid group: (meth) acrylic acid ethylene oxide modified phosphate (as shown below) 0

CH2 = CHC00CH2CH20 — P—OH

I

OH 312 / Invention Specification (Supplement) / 92-03 / 91137460 20 200302258 (Methyl) Propionate-$ Yu Zhi (ch2 = chc〇〇ch2ch〇hch2〇h) (d) There are 2 hydroxides Compounds with 2 (meth) acryl groups: Epichlorohydrin di (meth) acrylate modified 1,6-hexanediol ester (ch2 = chc〇〇ch2ch〇hch2〇 (ch2) 6〇ch2ch〇 hch2〇c〇ch = c Η 2), epichlorohydrin modified di (meth) acrylate diethylene glycol ester (ch2 = chc〇〇ch2ch〇hch2〇 (ch2ch2〇) 2ch2ch〇hch2〇c〇ch = C Η 2), epichlorohydrin modified with di (meth) acrylate phthalate (as shown below) 〇Η

I ^ YCOOCH2CHCH2OCOCH = CH2 ^^ CCK3CH2CHCH2OCOCH = CH2

OH di (meth) acrylic epichlorohydrin modified propylene glycol (C Η 2 = C Η C〇CH2CH〇HCH2〇CHCH3CH2〇CH2CH〇HCH2〇C〇CH = CH2), neopentyl glycol diglycidyl ether Di (meth) acrylates (ch2 = chc〇ch2ch〇hch20ch2c (ch3) 2ch2〇ch2ch〇hch20c = ch2) We believe that these compounds pass through their (meth) acrylic acid The group can be compatible with the (meth) acryl group of the hardening resin, and through its hydroxyl group, it can be compatible with the ether bond or ionic group of the conductive polymer, and can prevent the two sides from aggregating separately. From such a viewpoint, a compound having a linear molecular shape and a hydroxyl group at the terminal of the molecule is preferred, and a compound having multiple hydroxyl groups in the molecule is particularly preferred. Molecules that are too large have poor mobility and cannot follow the shape change of both the curable resin and the conductive polymer, so they are ineffective as compatibilizers. Therefore, the average weight molecular weight determined by gel permeation chromatography (G P C) based on polystyrene 21 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258 ethylene is good. In addition, it is important to dissolve the solvent in the coating material until the volatilized state. In addition, it is an element that is easy to purchase and cost important. From this point of view, (ethyl ester and 4-hydroxybutyl (meth) acrylate are particularly preferred. It is also possible to use a hardening resin (compatibility of the compatibilizer) without using a compatibilizer. (Equivalent), hardened resin is used. However, the role as a compatibilizer of hardened tree will be too complicated due to its complicated structure. Therefore, even if it is used as hardening 3, 1 or Two linear (E-solubilizers are preferred. The above-mentioned compatibilizers or their equivalents increase the compatibility with the solid matter at the time of curing by 5% by weight. The amount of aggregates decreases, but the curing It is lowered, so its upper limit is about 3 Q% by weight. Of course, the types of resin, conductive polymer, and compatibilizer can be easily determined through experiments. In order to further change the effects of the present invention, the coating composition of the present invention Within the range, an oxidation inhibitor, an ultraviolet absorber, and a light stabilizer may be contained. In order to impart anti-glare properties to the coating layer, silicon oxide particles or acryl urethane resin may be added to the extent that it is not within the range. Tree Organic etc., organic 312 / inventory supplements) / 92-03 / 91137460 is 1X103 or less, it must be cheap until it is finished, and it is also practically methacrylic acid) 2-hydroxy acrylic acid can be used alone with 3 The reason why it does not work with other lipids and conductive polymers! In the case of resins, it is preferred that the 3) acrylic-acrylic acid-based phase is on top of the aforementioned coating composition. After using more, the hardness of the film will be improved depending on the hardening type and the desired performance, without antifoaming agents, smoothing agents, polymerization inhibitors, etc. The effect of the present invention is changed. Acid resin, silicone resin, or inorganic fine particles. 22 200302258 The coating composition of the present invention can be prepared by mixing the above components and dissolving them in a solvent. If a solvent remains after coating, the curing reaction will be slowed, the crosslinking density will be reduced, and it will be difficult to obtain a sufficient cured film. Therefore, those with high solvent viscosity and high boiling point are not suitable. From this viewpoint, as the solvent, general low-molecular-weight alcohols are preferred, and specifically, ethanol, propanol, and butanol are preferred. The proportion of solid matter in the coating composition is usually preferably 10 to 70 Mi%. The anti-charge hard coating film of the present invention can be obtained by coating the above-mentioned coating composition on a thermoplastic resin film. The thermoplastic resin film used in the anti-static hard coat film of the present invention is preferably a transparent sheet or film. Examples include polyester film, polyethylene film, polypropylene film, celluloid film, Diacetyl cellulose film, triethyl cellulose film, ethyl butyrate cellulose film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polyvinyl alcohol film, polystyrene film , Polycarbonate film, Polymethylpentyl film, Poly film, Polyether ketone film, Polyether master film, Polyetherimide film, Polyimide film, Fluorine resin film, Nylon film, Acrylic film, Polycycloolefin films such as polycyclopentadiene films, etc. In the present invention, triethylfluorinated cellulose films, which are widely used as a material for a polarizing plate of a liquid crystal display, are particularly characterized as having no optical anisotropy. (TAC film) is preferred. The TAC film is usually formed by a solution molding method, so it has poor planarity and high transparency. Therefore, it is very difficult to form a uniform coating layer without defects such as aggregation. In the present invention, when a uniform hard coat layer is formed on such a highly transparent thermoplastic resin film, it is particularly effective. 23 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258 The hard coating layer of the present invention can be applied to a thermoplastic resin film by applying the coating composition to a thermoplastic resin film using a suitable coating device, and then applying ultraviolet rays. Or formed by radiation. In order to obtain a coating having a high crosslinking density, it is preferable to remove the solvent as much as possible and then irradiate it with ultraviolet rays or radiation. As the coating device, a known coating device such as a micro gravure coater, a gravure coater, a Maya bar coater, and a die coater can be used. The viscosity and concentration of the coating composition at the time of coating can be adjusted to a suitable level depending on the coating apparatus used. The film thickness of the hard coating after hardening is usually 1 ~ 2Q // m, and preferably 2 ~ 1Q // m. If the film thickness is thicker, the effect of preventing charging is greater, but the transparency will be lowered or the hard-coated film tends to curl. Since the hard coating film of the present invention is used in a display with high transparency, the haze of the hard coating film (measured according to JISK 7 105) is less than 2.5%. Better, especially less than 1 · ◦%. From the viewpoint of considering both high transparency and charging prevention performance, the surface resistivity (based on JIS 6911) of the hard coating layer is preferably less than 1.QX1012 Ω, and particularly preferably less than ι · 〇χΐο1: ιΩ. . The present invention is exemplified below by way of examples, but these are not intended to limit the present inventors. In addition, the same compounds are used unless otherwise specified. In addition, "parts" and "%" in the examples are "weight parts" and "% by weight" respectively unless otherwise specified. [Embodiment] (Example 1) In Examples 1 to 6, the hardening resin is pentaerythritol tetramethacrylate, and the conductive polymer is a methacrylate copolymer containing a 4th ammonium salt group. (Supplement) / 92-03 / 91137460 200302258 When the amount of 2-hydroxyethyl methacrylate, which is a compatibilizing agent, is examined, it will be examined how it affects the subject of the present invention. . On one side of a 75 μm polyester film (A_430), manufactured by Toyobo Corporation, the following coating composition 1 was applied with a bar coater, and a 60 t hot air blower was applied. After diluting the diluent solvent, it was irradiated with UV light to obtain an antistatic hard coat film. The thickness of the coating layer at this time was 5 // m. (Coating composition 1) Hardening resin: pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., NK-ester A-TMMT) 46.5 parts conductive polymer: Aleksand PQ-5 0 B (Meth) acrylate copolymer containing 4th level ammonium salt, molecular weight: 3 X 1 0 4, methanol solution, solid matter 50%) 6 0 · 0 parts compatibilizer: 2-hydroxyethyl acrylate (Manufactured by Kyoeisha Oil Co., Ltd., Lite ester HOA, molecular weight: 116) 2 ·· ◦ initiator: Irgaqiu 1 8 4 (manufactured by Ciba Geigy) 3.5 solvent: ethanol 70 0 · 0 parts of additive: Silane-based surfactant: BYK-3 0 0 (by BAK Chemical Co., Ltd.) For the total liquid, 0.05 part of the coating composition is contained in the solvent ethanol, and other compounds are mixed under stirring. They are sequentially added and dissolved at room temperature until they are in a uniform state. (Example 2) Except that pentaerythritol tetraacrylate was changed to 56.5 parts and 2-hydroxyethyl acrylate was changed to 10 parts in Example 1, it is the same as Example 1 25 312 / Invention Specification (Supplement) ) / 92-03 / 91137460 200302258, the same method is used to prepare a hard coating film to prevent electrification. (Example 3) Except that the pentaerythritol tetraacrylate in Example 1 was changed to 60.5 parts and the 2-hydroxyethyl acrylate was changed to 6 parts, the same method as in Example 1 was used to prepare an anti-charge hard coating. Layer film. (Example 4) Except that the pentaerythritol tetraacrylate in Example 1 was changed to 61.5 parts and the 5-hydroxyethyl acrylate was changed to 5 parts, the same method as in Example 1 was used to prepare a hard coating for preventing charge. Layer film. (Example 5) In this example, another miscibility agent was used. An anti-charge hard coating film was prepared in the same manner as in Example 1 except that 20 parts of hydroxyethyl acrylate was used as a compatibilizer, and 20 parts of hydroxybutyl acrylate was used. (Example 6) This example is an example in which a high molecular weight is used as the conductive polymer. Except that the coating composition 1 was changed to the following coating composition 3, the same manner as in Example 1 was used to prepare a film for preventing hard-coating from being charged. (Painting composition 3) Curing resin: Pentaerythritol tetraacrylate 46.5 parts Conductive polymer: Shaftoma ST 3 6 0 0 (Mitsubishi Chemical Co., Ltd., (meth) containing a level 4 ammonium salt Acrylate copolymer, molecular weight: 10 X 1 0 4, methyl cellosolve-methanol solution, 35% of solid matter) 60.0 parts compatibilizer: 2-hydroxyethyl acrylate 2.0 0 parts 312 / Invention Specification (Supplements) / 92-03 / 91137460 26 200302258 Initiated! J: Ilgaqiu 1 8 4 3. 5 parts Solvent: ethanol 6 0 · 0 parts Additives: Silane-based surfactant: BYK -3 0 0 to 5 parts of total liquid (Example 7) Example 7 and Example 8 are the same as Example 4 when the blending amount of the conductive polymer is changed. Except that the coating composition 1 was changed to the coating composition 4 described below, the same manner as in Example 1 was used to prepare a film for preventing a hard coat layer from being charged. The comparison is made so that the total solid mass of the conductive polymer and the curable resin becomes 7 6 · 5 parts. (Coating composition 4) Curing resin: Pentaerythritol tetraacrylate 6 6 .5 parts Conductive polymer: Alconte PQ-5 ◦ B 2 0 · 0 parts Compatibility agent: 2-hydroxyethyl acrylate 5 · 0part initiator: Ilgaqiu 1 8 4 3 · 5 parts Solvent: ethanol 7 0 · 0 parts Additive: siloxane-based surfactant: BYK-3 0 0 to total liquid 0.05 parts (Example 8) Except that the pentaerythritol tetraacrylate in coating composition 4 was changed to 36 · 5 parts, and Alcond PQ-50 B was changed to 80 · 0 parts, the same method as in Example 1 was used. , To obtain a hard coating film to prevent charging. 27 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258 (Example 9) This example is an example using a polyfunctional acrylate as a compatibilizer. In the coating composition 1 used in Example 1, 20 parts of acrylic acid 2-hydroxyethyl acrylate was replaced by 20 parts of pentaerythritol pentaerythritol monohydroxy pentaacrylate, and this was used as coating composition 5 and implemented. Example 1 A coating was prepared in the same manner, and an anti-static hard coat film was produced. Pentaerythritol pentaerythritol monohydroxy ester with a molecular weight of 5 2 4 is S R-3 9 9 from Sadoma Company. (Example 10) In this example, a compound having a hydroxyl group is used alone as a curable resin system, and an example in which it is also used as a compatibilizing agent. Therefore, no additional miscibility was achieved! J. A coating was prepared in the same manner as in Example 1 except that the following coating composition 6 was used, and an anti-static hard coat film was prepared. (Coating composition 6) Hardening resin and compatibilizing agent: pentaerythritol triacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., NK-ester A-TMM-3, molecular weight: 298) 6 6 · 5 parts 6 0.0 parts 3 5 parts 7 〇. 〇parts 0.05 28 Conductive polymer: Alicond PQ-5 0 B Initiator: Ilgaqiu 1 8 4 Solvent: Ethanol additive: Siloxane surfactant: BYK-3 0 0 For the total liquid 312 / Invention specification (Supplement) / 92-03 / 91137460 200302258 (Example 1 1) A coating was prepared in the same manner as in Example 1 except that a triethylfluorene-based cellulose film was used as the transparent plastic film. Then, a hard-coating prevention film was produced. (Comparative Example 1) This is an example of a case where no compatibilizing agent is used at all. A coating was prepared in the same manner as in Example 1 except that the following coating composition 7 was used, and a film for preventing a hard coat layer from being charged was produced. (Painting composition 7) Hardening resin: Pentaerythritol tetraacrylate 6 6 .5 parts Conductive polymer: Alicond PQ-5 0 B 6 0 · 0 parts Initiator: Irgaqiu 1 8 4 3 · 5 parts solvent: ethanol 7 0 · 0 parts additive: siloxane-based surfactant: BYK-3 0 0 for total liquid Q · 0 5 parts (comparative example 2) This comparative example uses a low molecular weight cationic interfacial activity An example of an agent (Ilegang T 0 F-5 ◦ 1 _ CN (manufactured by Nippon Oil & Fats Co., Ltd.)) instead of a conductive polymer. A hard coating film was produced after preparing a coating in the same manner as in Example 1 except that the following coating composition 8 was used. (Coating composition 8) Hardening resin: pentaerythritol tetraacrylate 46.5 parts conductive polymer: Ai Legang T ◦ F-5 Q 1-CN (manufactured by Nippon Oil & Fats Co., Ltd.) 29 312 / Invention Specification (Supplement) ) / 92-03 / 91137460 200302258 20.0 Compatibility agent: 2-hydroxyethyl acrylate 2 0. 0 parts initiator: Ilgaqiu 184 3 · 5 parts solvent: ethanol 7 0. 0 parts additive: siloxane series Surfactant: BYK-3 0 0. 05 parts of total liquid (Comparative Example 3) This Comparative Example is an example using antimony doped tin oxide via ultrafine particles as a conductive agent. A coating was prepared in the same manner as in Example 1 except that the following coating composition 9 was used, and an anti-static hard coat film was prepared. (Painting composition 9) Curing resin: Pentaerythritol tetraacrylate 46.5 parts Conductive agent: S η 0 2 doped with antimony (volume average particle diameter 0. 0 9 5 // m) 2 0 · 0 parts Compatibility agent: 2-hydroxyethyl acrylate 2 0 · 0 parts Initiator: Ilgaqiu 1 8 4 3 · 5 parts Solvent: ethanol 7 〇 · Q parts Additives: Silane-based surfactant: BYK-3 0 0 The following evaluations were performed on 5 parts of total liquid 0 · Q for the coating compositions and anti-static hard coat films obtained in Examples 1 to 11 and Comparative Examples 1 to 3. (1) Cohesiveness of conductive polymer or hardening resin in coating composition 30 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258 • After the coating is prepared, the mesh is 2 0 " m Nylon mesh filter. Resin agglutination can be confirmed on the Internet. It is indicated as "Yes" and it is regarded as "Defective". (2) Transparency of the coated product Transparency is related to the degree of haze (h a z e) due to visible light transmittance, and has a great relationship with the sharpness of a high-definition, high-resolution screen. Therefore, the turbidity and transmittance of the film were measured using a turbidity agent (h a z e m e t er) manufactured by Toyo Seiki Co., Ltd. in accordance with J.K.S. K 7 1 Ο 5. Transparency was evaluated based on turbidity. If the turbidity is less than 1.◦%, it is considered to be "excellently good", if it is less than 1.0% to 2.0%, it is considered to be "good", and if it is greater than 2.0%, it is considered to be "bad". (3) The uniformity of the appearance of the coated product. Observe the backlight through a thin film and observe the presence or absence of agglomerates in the coating layer. The number of persons who recognize and feel the presence of foreign matter through visual inspection is 1 5 0 // m or more, which is 5 0 ◦ The number of aggregates in c τη2 is 1 5 ◦ // m or more. In 5 Q ◦ c m2, the number of agglomerates was considered to be “excellent” if less than five, “good” when five or more were under twenty, and “bad” when more than twenty. (4) Antistatic property Using a high resistivity meter (Hiresta-UP) manufactured by Mitsubishi Chemical Corporation, the surface resistivity (Ω) of the film was measured, and the antistatic property was evaluated based on the surface resistivity. Those with a surface resistivity of less than 1. Q X 1 〇 1 1 Ω are considered to be “excellent”, 1.0X1011 or more and 1.0 × 1012 Ω is less than “good”, and 1.QX1012 Ω or more is considered “bad”. (5) Pencil hardness (hard-coating property) The pencil hardness tester made by Toyo Seiki Co., Ltd. was used to determine the film hardness in accordance with JI s K 5 4 0 0 31 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258 Pencil hardness. Those with a pencil hardness of "Η" are considered "good", and those with a pencil hardness of "B" are considered "bad". (6) Prevent the continuity of the charging effect. After placing the hard coat film in a dryer at 90 ° C for 250 hours, an oily substance will appear on the surface of the hard coat layer. It can be confirmed that the conductive agent has exuded. The case is "Yes", and the case that cannot be confirmed is "None". In the case of "yes", it is considered as "bad". The evaluation results are shown in Table 1 below. 32 312 / Invention Manual (Supplement) / 92-03 / 91137460 200302258 Table 1 Uniformity of Appearance of Transparent Coated Products (Resin Cohesive Coatings in Coatings) (Unit / 500cm2) Anti-Charging (Ω / Π) Persistent haze (%) Transmission resistance (%) of pencil hardness preventing charging effect Example 1 Μ 0.80% 92.0 1 5 X1010 Η None Example 2 Μ 川 \ 0.80% 92.0 7 5 X1010 Η Μ J \ w Example 3 No 0.80% 92.0 7 5 χΙΟ10 Η and y > Example 4 No 0.80% 92.0 7 5 ΧΙΟ10 Η Ατττ 1111 ~ Example 5 Μ «M 0.80% 92.0 1 5 ΧΙΟ10 Η Μ j \ w Example 6 No 0.80% 92.0 1 3 xlO10 迦 j \\\ Example 7 and J \ \\ 0.80% 92.0 0 5 χ1011 2 并 j \ \\ Example 8 Μ 0.80% 92.0 3 1 ΧΙΟ10 Η j \\\ Example 9 Μ j \ \\ 1.60% 91.9 11 3 ΧΙΟ10 Η Μ Example 10 and 1.30% 92.0 7 7 ΧΙΟ10 Η No Example 11 No 0.20% 92.3 6 5 ΧΙΟ10 Η Μ j \\\ Comparative Example 1 There are 2.80% 91.9 124 5 ⅩΙΟ10 ΗComparative example 2 and M 1.80% 92.0 15 2 ΧΙΟ11 Η There is comparative example 3 Μ J »ΝΝ 5.00% 84.0 1 3 ΧΙΟ8 2 Μ j 33 312 / Description of the Invention (Supplement) / 92-03 / 91137460 200302258 In Table 1, it can be seen that compared with Comparative Example 1 which does not contain a compatibilizer at all, Examples 1 to 5 containing a compatibilizer, aggregates in the coating The uniformity of the appearance and transparency (turbidity) of the coated product are extremely excellent. In addition, Comparative Example 2 using a low-molecular-weight surfactant as the conductive agent is compared with Examples 1 to 5. By using the conductive polymer of the present invention, the effect of preventing the electrification is continuously seen even at high temperature and for a long time. To have a very significant effect. It can be seen that when the hardening resin is pentaerythritol tetraacrylate, the conductive polymer is an acrylate copolymer containing a 4th ammonium salt group, and the compatibilizing agent is hydroxyethyl acrylate, and 5% of the solid matter containing the film In the case of the above-mentioned miscible agent, the agglutination property can be remarkably improved. It was also found that the amount of the conductive polymer used in the curable resin has a specific and appropriate range. In this case, a blending amount of 1 ◦ to 40% is appropriate. It is also known that if the hard coating layer is formed by coating with a coating composition within this range, a hard coating film having excellent transparency, antistatic properties, uniformity, abrasion resistance, and chemical resistance can be obtained. . 312 / Invention Specification (Supplement) / 92-03 / 91137460

Claims (1)

200302258 Patent application scope 1 · A coating composition, characterized in that it is composed of an ultraviolet or radiation hardening resin having at least three (meth) acryl fluorene groups, a conductive polymer, and one or two The (meth) acrylfluorenyl group and a compatibility agent containing at least one hydroxyl group, and the ultraviolet or radiation hardening resin may not contain the compatibility agent when it contains a hydroxyl group in its molecule. 2. The coating composition according to item 1 of the patent application range, in which the molecular weight of the conductive polymer is 2 X104 to 50 X104, which is a polyether, a polymer having a * level 4 ammonium salt group, and a polymer containing sulfonic acid. Either a polymer or a high-molecular charge-transporting polymer, the compatibilizing agent is an ultraviolet- or radiation-reactive monomer or an oligomer having a molecular weight of 1 X 103 or less, and is hardened with respect to the coating composition. The proportion of the compatibilizing agent or its equivalent of the solid matter at the time is 5% by weight or more. 3. The coating composition according to item 2 of the patent application range, wherein the conductive polymer is a polymer containing a level 4 ammonium salt group. 4. The coating composition according to item 3 of the scope of patent application, wherein the aforementioned polymer containing a level 4 ammonium salt group is a (meth) acrylate copolymer containing a level 4 money salt group. 5. The coating composition according to any one of claims 1 to 4, wherein the proportion of the aforementioned conductive polymer with respect to the solid matter at the time of curing of the aforementioned coating composition is 10 to 40% by weight. . 6 · An anti-charge hard coating film, characterized in that it has a coating composition coated with any one of claims 1 to 4 on at least one side of a thermoplastic resin film by applying ultraviolet rays Or radiation irradiation and 35 312 / Invention Specification (Supplement) / 92-03 / 91137460 200302258 is hardened to form a conductive hard coat layer. 7 · A hard-coating film for preventing electrification, which is characterized in that it has at least one side of a thermoplastic resin film coated with a coating composition according to item 5 of the patent application and is hardened by irradiation with ultraviolet rays or radiation. Forms a conductive hard coat. 8 _ The anti-charge hard coating film according to item 6 of the patent application scope, wherein 'the aforementioned thermoplastic resin film is triethylfluorene-based cellulose. 9 · The anti-charge hard coating film according to item 7 of the scope of patent application, wherein the thermoplastic resin film is triethylfluorene-based cellulose. 36 312 / Description of the Invention (Supplements) / 92-03 / 91137460 200302258 Lu, (1), the designated representative of the case is: Figure _ (B), the representative symbol of the element of the representative diagram is briefly explained: ίΚ 柒, if the case If there is a chemical formula, please disclose the chemical formula that best shows the characteristics of the invention: 312 / Invention Specification (Supplement) / 92-03 / 91137460 4