JPH01135875A - Coating agent for plastic - Google Patents

Abstract

PURPOSE:To obtain the above coating agent, containing a metallic oxide (fine particles) in an aqueous resin dispersion prepared by emulsion polymerizing a polymerizable monomer using a specific polyamine based reactive surfactant as an emulsifying agent and having excellent adhesion on plastic substrates. CONSTITUTION:The aimed coating agent containing (A) an aqueous resin dispersion obtained by emulsion polymerizing (iv) a polymerizable monomer component in an aqueous medium using a reactive surfactant prepared by reacting (i) a polyamine compound having >=2 primary and/or secondary amino groups in the molecule with (ii) a compound expressed by formula I (R is 4-28C hydrocarbon; A is 2-4C alkylene; n is 0-30; X is functional group or atomic group reactive with the amino group) and, as necessary, further (iii) a compound expressed by formula II (R' is polymerizable unsaturated group) as an emulsifying agent and (B) a metallic oxide (fine particles) at 100:0-30:70 weight ratio of the components (A) to (B).

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a coating agent for plastics that is useful as an anchor agent, primer, protective coating agent, cosmetic coating agent, functional coating agent, etc. for various plastic molded products, sheets, films, etc. be. [Prior art and problems to be improved by the present invention]
In recent years, the application of plastics to various fields has been expanding more and more, and the requirements for performance have also tended to become more sophisticated and diversified. Among the performances required of plastic products, surface performance is one of the most important ones, and various coating agents are used to improve surface performance, impart specific functions, impart beauty, and the like. Various polymeric compounds are used as a vehicle for the coating agent, and the polymeric compound or its precursor is used in the form of a solution or dispersion of the polymeric compound or its precursor in an organic solvent and/or water, or in the form of a solvent-free solution. Among the above forms of coating agents, organic solvent type ones have relatively good performance and have a wide range of applications, but organic solvents impregnate the substrate and deteriorate the physical properties. Since the aqueous dispersion type does not have the drawbacks mentioned above, future development is expected, but at present, there are no aqueous coating agents available.
It has drawbacks such as insufficient adhesion to the substrate and poor water resistance, which limits its range of applications. An object of the present invention is to develop a water-based coating agent that adheres well to difficult-to-adhere plastics such as polyethylene terephthalate and has excellent water resistance and durability. [Means and effects for solving the problem] The present inventors have discovered that an aqueous resin dispersion obtained by emulsion polymerization of a polymerizable monomer using a polyamine-based reactive surfactant having a specific structure as an emulsifier. In addition, by using fine particles of metal oxide and/or metal hydroxide, adhesion can be improved and static electricity, which is often a problem in plastic materials, can be achieved. The present invention was completed based on the discovery that the effect of preventing electrification is improved. That is, the present invention provides polyamine compounds having two or more primary and/or secondary amino groups in the molecule (wherein R represents a hydrocarbon having 4 to 28 carbon atoms, and A represents a hydrocarbon having 2 to 4 carbon atoms). represents an alkylene group, n represents O or an integer of 1 to 30,
X represents an atomic group having a functional group that can react with an amino group. ) and, if necessary, the compound represented by the general formula (
In the formula, R' represents an atomic group having a polymerizable unsaturated group, and X represents an atomic group having a functional group capable of reacting with an amino group. )
An aqueous resin dispersion obtained by emulsion polymerization of a polymerizable monomer component consisting of a polymerizable monomer (5) in an aqueous medium using a reactive surfactant obtained by reacting a compound represented by as an emulsifier ( Em) and fine particles (M) of metal oxide and/or metal hydroxide, the aqueous resin dispersion [
This invention relates to a coating agent for plastics, characterized in that the content ratio of (Em) and the fine particles CM) is in the range of (Em): (M) = 100:O to 30Nia0 in solid weight ratio. . The polyamine compounds having two or more primary and/or secondary amino groups in the molecule used in the present invention are amines having two or more primary and/or secondary amino groups in the molecule. or its derivatives, such as polyalkyleneimines obtained by polymerization or copolymerization of alkyleneimines such as polyethyleneimine obtained by polymerization of ethyleneimine; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc. (poly)alkylene polyamine; polyamide polyamine obtained by condensation of polyalkylene imine and/or (poly) alkylene polyamine with polybasic acid such as adipic acid; polyalkylene imine and/or (poly) alkylene polyamine and/or alkylene Examples include polyurea polyamines obtained by reaction of imine and urea; polyamide polyester polyamines obtained by copolymerization of alkylene imine and acid anhydride such as phthalic acid. Further, as polyamine derivatives, alkylene oxides such as ethylene oxide and propylene oxide, (meth)acrylic acid esters such as butyl acrylate and methyl methacrylate, α,β-unsaturated acid amide compounds such as acrylamide, etc. are added to the polyamine. Examples include things that have been reacted with. In the present invention, it is preferable to use polyethyleneimine or a derivative thereof as the polyamine compound in order to obtain excellent surface activity. Further, in consideration of the water solubility, solution viscosity, and surfactant ability of the resulting reactive surfactant, it is preferable to use polyethyleneimine having a molecular weight of 5000 or less. In the compound (hereinafter referred to as compound (1)) represented by the general formula % formula % (in which R, A, X and n are the same as above) used in the present invention, a compound corresponding to R in the formula Examples of hydrocarbon groups having 4 to 28 carbon atoms include linear or branched alkyl groups having 4 to 28 carbon atoms, (alkyl)aryl groups, (alkyl)hydrogenated aryl groups, (alkyl)aralkyl groups, etc. can be mentioned. As the compound (1), for example, n-
Octyl polyoxyalkylene glycidyl ether, n
-Nonyl polyoxyalkylene glycidyl ether, lauryl polyoxyalkylene glycidyl ether, stearyl polyoxyalkylene glycidyl ether, 2-
Primary alkyl polyoxyalkylene glycidyl ethers such as ethylhexyl polyoxyalkylene glycidyl ether; those obtained by adding 1 to 30 moles of alkylene oxide to a mixture of secondary alcohols having 12 to 14 carbon atoms and further glycidyl etherification, carbon number 10
Secondary alkyl polyoxyalkylene glycidyl ethers, such as those obtained by adding 1 to 30 moles of alkylene oxide to a mixture of 1 to 12 secondary alcohols and further glycidyl etherification; Alkylphenyl polyoxyalkylene glycidyl ethers such as octylphenyl polyoxyalkylene glycidyl ether, nonylphenyl polyoxyalkylene glycidyl ether, lauryl phenyl polyoxyalkylene glycidyl ether, and stearyl phenyl polyoxyalkylene glycidyl ether; the number of moles of alkylene oxide added is 1 30 octylcyclopentyl polyoxyalkylene glycidyl ether, octylcyclohexyl polyoxyalkylene glycidyl ether, nonylcyclopentyl polyoxyalkylene glycidyl ether, nonylcyclohexyl polyoxyalkylene glycidyl ether, laurylcyclopentyl polyoxyalkylene glycidyl ether, laurylcyclohexyl polyoxyalkylene glycidyl ether , stearyl cyclopentyl polyoxyalkylene glycidyl ether, stearyl cyclohexyl polyoxyalkylene glycidyl ether, and other alkylcycloalkyl polyoxyalkylene glycidyl ethers; octylbenzyl polyoxyalkylene glycidyl ether, nonylbenzyl poly, with an added mole number of alkylene oxide of 1 to 30; Alkylbenzyl polyoxyethylene glycidyl ethers such as oxyalkylene glycidyl ether, lauryl benzyl polyoxyalkylene glycidyl ether, stearyl benzyl polyoxyalkylene glycidyl ether; octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether, 2-ethylhexyl glycidyl ether Glycidyl ethers of higher alcohols such as octylphenyl glycidyl ether, nonylphenyl glycidyl ether, lauryl phenyl glycidyl ether, stearyl phenyl glycidyl ether; octylcyclopentyl glycidyl ether, octylcyclohexyl glycidyl ether, nonylcyclopentyl Glycidyl ethers of alkylcycloalkanols such as glycidyl ether, nonylcyclohexylglycidyl ether, laurylcyclopentylglycidyl ether, laurylcyclohexylglycidyl ether, stearylcyclopentylglycidyl ether, and stearylcyclohexylglycidyl ether; octylbenzylglycidyl ether, nonylbenzylglycidyl Glycidyl ethers of alkylbenzyl alcohols such as ether, lauryl benzyl glycidyl ether, and stearyl benzyl glycidyl ether; α-olefin epoxides having 12 or 14 carbon atoms, and 16 or 18 carbon atoms
1,2-epoxy alkanes such as α-olefin epoxide; alkyl isocyanates such as octyl isocyanate, decyl isocyanate, and octadecyl isocyanate; alcohols such as octatool, lauryl alcohol, and stearyl alcohol, or alkylene oxide adducts of these alcohols. Monoisocyanate compounds obtained by the reaction of and diisocyanates such as tolylene diisocyanate; Halides substituted with halogen atoms such as iodine; Saturated fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid; Unsaturated fatty acids such as oleic acid, linoleic acid, linoleic acid, and eleostearic acid; ( 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylate
Examples include (meth)acrylic esters such as stearyl acrylate, and one or more selected from these groups can be used. The compound (
The amount of 1') used is not particularly limited, but in order to develop sufficient surface activity, it is preferable to use 0.01 to 0.9 molecules of compound (1) per active amine hydrogen of the polyamine compound. . In the present invention, the general formula (in the formula R
', X are the same as above. ) (hereinafter referred to as compound (II)), the polymerizable unsaturated group in the atomic group corresponding to R' in the formula includes (meth)acryloyl group, (meth)allyl group, vinyl group etc. can be mentioned. The compound (If) is (meth)
(meth) having a group that reacts with an amino group in the molecule, such as 2-chloroethyl acrylate, glycidyl (meth)acrylate, and 2-incyanate ethyl (meth)acrylate.
Acrylic acid esters; vinyl ethers such as chloroethyl vinyl ether; (meth)allyl chloride, (
Meta)allyl bromide, (meth)allyl isothiocyanate, allyl (meth)acrylate, half ester of (meth)allyl alcohol and dicarboxylic acid anhydride such as phthalic anhydride or succinic anhydride, (meth)allyl glycidyl ether, etc. (meth)allyl compounds; styrene derivatives that have a group that reacts with an amine group in the empty molecule such as chloromethylstyrene and α-methylchloromethylstyrene; groups that react with an amino group in the molecule such as vinyl chloroacetate Vinyl esters of acids having the following can be mentioned, and one or more kinds selected from these groups can be used. In order to obtain a reactive surfactant in good yield, it is preferable to use vinyl ethers, (meth)allyl compounds, styrene derivatives, and vinyl esters of organic acids as the compound (■). Compound (n) is not an essential component in the present invention, but
By adding compound (II) to the polyamine compound, polymerization reactivity is introduced into the reactive surfactant, and when the polymerizable monomer component is polymerized using this as an emulsifier, the resulting polymer and emulsifier are integrated, and therefore It is a preferred embodiment of the present invention to use a semi-compound (■) which has the effect of improving the water resistance and adhesion of the aqueous resin dispersion. The amount of compound (n) used is per active amine hydrogen of the polyamine compound. 9
It is preferable to set it as 0.01-0.9 molecules. The reaction conditions for obtaining the reactive surfactant used in the present invention are not particularly limited, and for example, the polyamine compound, compound (+), and compound (II) may be diluted with a solvent as is or if necessary, Preferably room temperature to 200°
C1 can be synthesized by reaction under a temperature condition of preferably 50 to 100°C. At this time, it is preferable that the solvent used if necessary be capable of dissolving the polyamine compound, compound (1) and compound (II), and be inert to them. Further, during the reaction, a catalyst may be freely used to promote the reaction. The reactive surfactant thus obtained can be mixed with an acid to form a salt. It is preferable to use a salt because it improves solubility in water. Acids that can be blended include:
Inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as formic acid, acetic acid and (meth)acrylic acid. The polymerizable monomer diagram used in the polymerizable monomer component in the present invention is not particularly limited as long as it contains a polymerizable unsaturated group, but examples include methyl (meth)acrylate, Ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2-ethylhexyl, lauryl,
Straight chain or branched aliphatic alkyl alcohol or alicyclic alkyl alcohol having 1 to 18 carbon atoms such as stearyl or cyclohexyl ester and (meth)
(Meth)acrylic acid esters, which are ester compounds with acrylic acid; polymerizable compounds such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid, or monoester compounds of maleic acid or fumaric acid. Unsaturated carboxylic acids and their salts; polymerizable unsaturated sulfonic acids and their salts such as vinyl sulfonic acid, styrene sulfonic acid, sulfoethyl (meth)acrylate; aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate , dimethylaminoethyl (meth)acrylamide, vinylpyridine, vinylimidazole, vinylpyrrolidone and other basic unsaturated monomers; (
Hydroxyl group-containing unsaturated monomers such as hydroxyethyl meth)acrylate, hydroxypropyl (meth)acrylate, and monoesters of (meth)acrylic acid and polypropylene glycol or polyethylene glycol; glycidyl (meth)acrylate, etc. Epoxy group-containing unsaturated monohydric compounds; (meth)acrylic acid 2-hydroxy-
Halohydrin group-containing unsaturated monomers such as 3-chloropropyl; blocked incyanate group-containing unsaturated monomers such as a phenolic adduct of incyanatoethyl (meth)acrylate; (meth)acryloylaziridine; (
Aziridinyl group-containing unsaturated monomers such as meth)acryloyloxyethylaziridine; 2-produnyl-2-
Oxazoline group-containing unsaturated monomers such as oxazoline and 2-vinyl-2-oxazoline; (meth)acrylic acid and ethylene glycol, 1,3-butylene glycol,
Polyfunctional (meth) containing two or more polymerizable unsaturated groups in the molecule, such as esters with polyhydric alcohols such as 1,6-hexane glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, and trimethylolpropane. Acrylic esters; (meth)acrylamide, methylolated (meth)acrylamide,
(Meth)acrylamides such as alkoxymethylolated (meth)acrylamides having 1 to 4 carbon atoms; vinyltrimethoxysilane, vinyltriethoxysilane, y-
Organosilicon monomers such as (meth)acryloxypropyltrimethoxysilane, allyltriethoxysilane, trimethoxysilylpropylallylamine; and styrene,
Vinyl toluene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, ethylene, propylene, butacynine, iso\lene, dicyclopentadiene, divinylbenzene, diallyl phthalate etc., and one type or a mixture of two or more types selected from these groups can be used. The aqueous resin dispersion of the present invention emulsifies a polymerizable monomer component consisting of one or more of the polymerizable monomers in an aqueous medium using the above-mentioned reactive surfactant as an emulsifier. It is obtained by polymerization. Emulsion polymerization can be carried out according to a known method using a known polymerization initiator and various other additives if necessary. During emulsion polymerization, the type of reactive surfactant used as an emulsifier is not particularly limited, but polymerizable monomer 10
It is preferable to use it in a range of 0.5 to 200 parts by weight relative to 0 parts by weight. Further, although it is preferable to use the above-mentioned reactive surfactant alone as an emulsifier, it is also possible to use a conventionally known emulsifier in combination to the extent that the characteristics of the present invention are not impaired. Furthermore,
After emulsion polymerization, a PH adjuster, curing catalyst, diluent, etc. can be added if necessary. The aqueous resin dispersion of the present invention has low foaming and excellent long-term stability, and the film formed by volatilizing water from the aqueous resin dispersion has excellent adsorption and adhesion to various plastics. It has excellent physical properties such as adhesion, water resistance, and strength, but in addition, the polymerizable monomer component used in emulsion polymerization has at least one functional group that can react with the amine group of the glaze. By including body (A-1), the above-mentioned characteristics are more prominently exhibited. Examples of functional groups that can react with the amino group of the reactive surfactant include carboxyl group, sulfonic acid group, aziridinyl group, oxazoline group, hydroxyl group, epoxy group,
Examples of the polymerizable monomer (A-1) having these functional groups include halohydrin groups, blocked isocyanate groups, and alkoxysilyl groups. Carboxylic acids, polymerizable unsaturated sulfonic acids, aziridinyl group-containing unsaturated monomers,
Oxazoline group-containing unsaturated monomers, hydroxyl group-containing unsaturated monomers, halohydrin group-containing unsaturated monomers, blocked incyanate group-containing unsaturated monomers, epoxy group-containing unsaturated monomers and organosilicon monomers. The metal oxide and/or metal hydroxide fine particles CM) used in the present invention have element symbols S i , T i ,
AA! . Sb, Zr, Ce, V, Nb, Ga, In, Fe, h
In, Ni, Co, Ta, Sn. It is a fine particle of hydroxide or oxide containing one or more metals represented by Mg and W, and the particle size of a single particle is 1 nm-11000 rL. These fine particles CM) may be either missing particles or secondary particles which are aggregates thereof, and may be in any state of powder or sol dispersed in water and/or organic solvent such as hydrosol or organosol. But it can be used. The fine particles CM) may be a hydroxide or oxide of a single metal, or a composite hydroxide or oxide of two or more metals. The usage ratio of aqueous resin dispersion (Em) and fine particle CM) is as follows:
Weight ratio of solid content: (Em): (M) = 100
:0~30 Near 0 range. Use of fine particles CM, l Even if i4- is O, a coating agent for plastics with excellent adhesion, water resistance, and durability can be obtained, but fine particles [
By using M] in combination, the adhesion to plastics and antistatic properties can be improved. Fine particles (
The usage amount of M) is (Em): CM) = 30 near 0
If the amount is too large, the film becomes brittle and its performance as a coating agent decreases, which is not preferable. The coating agent for plastics of the present invention can be produced by simply mixing the aqueous resin dispersion (Em) and the fine particles CM), but if necessary, a heating operation may be added. aqueous resin dispersion in the presence of (
It can also be produced by the method of producing Em). The coating agent for plastics of the present invention can be used as an anchor agent, a primer coating agent, and a primer coating agent for each sleeve plastic.
It can be used as a top coat agent and an antistatic treatment agent, and a coating film with excellent adhesion, water resistance, solvent resistance, durability, and antistatic properties can be obtained.
A colored coating agent may be obtained by adding pigments or dyes, and a functional coating agent may be obtained by adding a functional agent such as a conductive substance, a light transmittance control substance, or a lubricity improver. Furthermore, if necessary, known PH regulators, viscosity regulators, antifoaming agents, preservatives, etc. can be added. [Effects of the Invention] The coating agent for plastics of the present invention comprises an aqueous resin dispersion (CEm) obtained by emulsion polymerization of a polymerizable monomer using a reactive surfactant having a presumed structure as an emulsifier and a metal oxidation agent. Because it contains a certain ratio of fine particles (M) of metal hydroxide and/or metal hydroxide, it has excellent adhesion to various general-purpose and engineering plastics, including hard-to-adhesive plastics such as polyethylene terephthalate. The resulting coating has excellent properties such as water resistance, hot water resistance, durability, and antistatic properties. Therefore, the coating agent for plastics of the present invention is useful as a vehicle for printing polyethylene terephthalate film, aluminum vapor deposition, a primer for magnetic coating, antistatic treatment, and surface roughening coating.
It can be effectively used as a cosmetic, protective, and functional coating agent for BS, polyolefin, polycarbonate, acrylic resin, polybutylene terephthalate (PBT), and other molded products, sheets, and films. [Examples] The present invention will be explained in detail below using Examples, but the scope of the present invention is not limited only to these Examples. In the examples, unless otherwise specified, % indicates weight %, and parts indicate parts by weight. Reference Example 1 45 parts of polyethyleneimine (Evomin 5P-006, manufactured by Nippon Shokubai Kagaku Kogyo ■, average molecular weight approximately 600) was placed in a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser. 14.7 parts of a mixture of α-olefin epoxides having 12 and 14 carbon atoms (AOE-X24, manufactured by Daicel Chemical) was charged, heated to 80°C while gently blowing nitrogen gas, and reacted for 4 hours to form a reactive interface. An activator (1) was obtained. Reference Examples 2 to 6 In Reference Example 1, the polyamine compounds, compound (1) and compound (If) shown in Table 1 were used, and the reaction times were as shown in Table 1. The same operation as in Example 1 was repeated to obtain reactive surfactants (2) to (6). Reference Example 7 In the same flask as used in Reference Example 1, 100 parts of polyethyleneimine (Epomin 5P-012. manufactured by Nippon Shokubai Chemical Co., Ltd., average molecular weight 1200) and 50 parts of stearic acid were added.
1 part and 70 parts of xylene were charged, and the mixture was heated to 140° C. while slowly blowing nitrogen gas to perform dehydration and bonding over 4 hours. After the reaction was completed, xylene was distilled off to obtain a reactive surfactant (7). Example 1 5 parts of the reactive surfactant (1) obtained in Reference Example 1 and 100 parts of water were charged into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction pipe, a thermometer, and a reflux condenser, and the mixture was stirred. A homogeneous aqueous solution was obtained, the pH was adjusted to 4.5 with acetic acid, and then diluted with water to a total amount of 167 parts. As a polymerization catalyst, 3 parts of a 10% aqueous solution of 2,2'-azobis(2-methylpropanediamine) dihydrochloride was charged, heated to 65°C while gently blowing nitrogen gas, and stirred to form a uniform aqueous solution. A previously prepared monomer mixture consisting of 50 parts of methyl methacrylate and 50 parts of butyl acrylate was added dropwise thereto over a period of 2 hours using a dropping funnel. Thereafter, the temperature was maintained at 65°C and the mixture was further stirred for 1 hour to obtain an aqueous resin dispersion [1] with a nonvolatile content of 38.7% and a pH of 5.3. Examples 2 to 6 Examples 2 to 6 were the same as in Example 1, except that the type of reactive surfactant, the amount and type of PH adjuster, and the type of polymerizable monomer component were as shown in Table 2. The same operation as in 1 was repeated to obtain aqueous resin dispersions [2] to [6]. The results are summarized in Table 2. Comparative Example 1 The same procedure as in Example 1 was repeated except that the same amount of the commercially available cationic emulsifier shown in Table 2 was used instead of the reactive surfactant as the emulsifier. An aqueous resin dispersion [1'] was obtained. The results are summarized in Table 2. Example 8 100 parts of the aqueous resin dispersion (3) obtained in Example 3 was mixed with 194 parts of "Snowtenx AKJ" (manufactured by Nichiwa Kagaku Co., Ltd., concentration 20%), which is a hydrosol of silica fine particles surface-modified with alumina. Add and mix at room temperature to reduce the non-volatile content to 26
A related aqueous resin dispersion [8] was obtained. Example 9 100 parts of the aqueous resin dispersion (6) obtained in Example 6 was mixed with "Alumina Sol-100", which is an alumina hydrosol.
(manufactured by Nichiryo Kagaku side, particle size 1010 x 100n concentration 10
%) and mixed at room temperature to form an aqueous resin dispersion with a non-volatile content of 14.

[9] was obtained. Example 10 To 100 parts of the aqueous resin dispersion (7) obtained in Example 7, 390 parts of titania sol (a hydrosol containing 5 parts of titania with a particle size of 2 to 3 nm) was added and mixed at room temperature to reduce the nonvolatile content to 1 part.
A 2% aqueous resin dispersion [10] was obtained. Example 11 Aqueous resin dispersions [1] to [1] obtained in Examples 1 to 10 were applied to a polyethylene terephthalate film (hereinafter referred to as PET film) having a thickness of 20 μm and not subjected to surface treatment.
0] and comparative aqueous resin dispersion obtained in Comparative Example 3 [1
'] was coated with a bar coater to a dry film thickness of 1 μm, and dried by heating at 110° C. for 1 minute. The adhesion and hot water resistance of the resulting coating layer were tested. The test results are shown in Table 3. Adhesion: After adhering cellophane tape to the coating surface, it was peeled off at once in a 90° direction, and evaluated from 10 points (no peeling) to 1 point (full peeling) depending on the degree of peeling of the coating layer. Hot water resistance: 90~9 coated with 9 PET film
After being immersed in hot water at 5° C. for 30 minutes, the water on the surface was wiped off and an adhesion test was conducted in the same manner as above. Example 12 The surface electrical resistance of the coated PET lid obtained in Example 11 was measured at 23° C. and 65% rtH. The results are shown in Table 4. Table 4 Example 13 was applied to various plastic plates (thickness: 2 mm%, surface untreated) to a thickness of about 10 μm, and after drying at 80° C. for 10 minutes,
An adhesion test was conducted. The results are shown in Table 5. In the table,
The upper row shows the adhesion under normal conditions, and the lower row shows the adhesion after being immersed in tap water at room temperature for 24 hours. Table 5

Claims (3)

[Claims] (1) General formulas for polyamine compounds having two or more primary and/or secondary amino groups in the molecule include mathematical formulas, chemical formulas, tables, etc. hydrogen, A represents an alkylene group having 2 to 4 carbon atoms, and n is 0 or 1 to 30
represents an integer of , and X represents an atomic group having a functional group that can react with an amino group. ) and, if necessary, a compound represented by the general formula R'-X (wherein R' represents an atomic group having a polymerizable unsaturated group,
represents an atomic group having a functional group that can react with an amino group. ) An aqueous resin dispersion obtained by emulsion polymerization of a polymerizable monomer component consisting of a polymerizable monomer (A) in an aqueous medium using a reactive surfactant obtained by reacting a compound represented by (A) as an emulsifier. [Em] and fine particles [M] of metal oxide and/or metal hydroxide, the content ratio of the aqueous resin dispersion [Em] and the fine particles [M] is the weight ratio of the solid content [ A coating agent for plastics, characterized in that Em]:[M]=100:0 to 30:70. (2) The plastic according to claim 1, wherein the polymerizable monomer component comprises a polymerizable monomer (A-1) having a functional group capable of reacting with an amino group. coating agent. (3) Polyamine compounds in which the reactive surfactant has two or more primary and/or secondary amino groups in the molecule have general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R is carbon Represents a hydrocarbon having 4 to 28 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and n is 0 or 1 to 30
represents an integer of , and X represents an atomic group having a functional group that can react with an amino group. ) and the general formula R'-X (wherein R' represents an atomic group having a polymerizable unsaturated group,
represents an atomic group having a functional group that can react with an amino group. ) The coating agent for plastics according to claims 1 and 2, which is obtained by reacting with a compound represented by: