JP2001342381A - Coating agent and coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent excellent in heat resistance and flame retardancy. SOLUTION: The coating agent is characterized in that it comprises a metal containing ethylenic unsaturated polymer (A) described by general formula (1) and another ethylenic unsaturated monomer (B). [In the general formula (1), M denotes a 2-4 valent metal; R1 denotes a hydrogen atom or a methyl group ; m denotes a 2-4 integer; X denotes -O-(R2O)n-, -CO-O-(R2O)n-, -CO-O-(R2 O)n-CO-R3-CO-O-, -CH2O-(R2O)n, or -CH2O-CO-R3-CO-O-, wherein n denotes a 1-8 integer ; R2 is an alkylene group having 2-4 carbons; R denotes an alkylene group having 2-4 carbons or an alkenylene group having 2-4 carbons.].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating agent and a coated object having excellent heat resistance and flame retardancy.

[0002]

2. Description of the Related Art Conventionally, as a coating resin used for hardening the surface of a plastic or the like, a method of coating by applying heat energy, an organosiloxane resin or a melanin resin, or a method of coating by ultraviolet irradiation. (For example, Japanese Patent Publication No. 6-87129).

[0003]

However, the above coating agents do not have heat resistance and flame retardancy.
For this reason, there is a problem in that there are many restrictions on the use of molded articles, films, sheets, and the like for home appliances that require heat resistance and flame retardancy.

[0004]

Means for Solving the Problems The present inventors have found that heat resistance,
As a result of intensive studies on a coating agent having excellent flame retardancy, the present invention has been achieved.

That is, the present invention is characterized by comprising a metal-containing ethylenically unsaturated monomer (A) represented by the following general formula (1) and another ethylenically unsaturated monomer (B). It is a coating agent.

[0006]

Embedded image

Wherein M is a divalent to tetravalent metal, R ¹ is a hydrogen atom or a methyl group, m is an integer of 2 to 4, and X is —O— (R ²
O) n -, - CO- O- (R 2 O) n-, -CO-O- (R 2 O) n-CO-R 3 -CO-O-, -CH 2 O- (R 2 O) n- or ^{_{-CH 2 O-CO-R 3}} -C
N represents an integer of 1 to 8, R ² represents an alkylene group having 1 to 4 carbon atoms, and R ³ represents an alkylene group having 2 to 4 carbon atoms or an alkenylene group having 2 to 4 carbon atoms. ]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), M is 2 to
A tetravalent polyvalent metal, such as Ib metal (eg, copper), IIa metal (eg, magnesium, calcium, barium), II
Metals b (eg, zinc), IIIa metals (eg, aluminum, gallium), IVa metals (eg, germanium, tin), IVb metals (eg, titanium), and Group VIII transition metals (eg, iron, cobalt, nickel). Of these, metals IIa, IIIa and IVb are preferred, and calcium, aluminum and titanium are particularly preferred. The M content in the general formula (1) is usually 1% by weight or more, preferably 3 to 20% by weight, particularly preferably 5 to 5% by weight from the viewpoint of the strength of a polymer using this monomer.
15% by weight.

R ¹ is a hydrogen atom or a methyl group, preferably a methyl group. R ² is an alkylene group having 1 to 4 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group, and a butylene group, and preferably an ethylene group. R ³ is an alkylene group having 2 to 4 carbon atoms or an alkenylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group. Examples of the alkenylene group having 2 to 4 carbon atoms include a vinylene group, a propynylene group, and a butynylene group. R ³ is preferably an ethylene group or a vinylene group. m is an integer of 2 to 4, preferably 3. n is an integer of 1 to 8, preferably 1 to 4
Is an integer. The X Specific for, for example, _{-O- (C 2 H 4 O)} 2 -, -CO-O- (C 2 H 4 O) 2 -, -CO-O- (C 2 H 4 O) 4 - _{, -CO-O- (C 2 H} 4 O) 2 -CO-C 2 H 4 -CO-O
—, —CH ₂ O— (C ₂ H ₄ O) ₂ ——CH ₂ O—CO—C ₂ H ₄ —CO—O— and the like.

As a method for producing the monomer represented by the general formula (1), for example, a method of reacting an alkylene oxide adduct of vinyl alcohol or an alkylene oxide adduct of (meth) acrylic acid with a polyvalent metal alkoxide is used. Is mentioned. Polyvalent metal alkoxide (C2-C2)
Examples of 4) include aluminum isopropoxide, aluminum ethoxide, and titanium isopropoxide. The amount of the polyvalent metal alkoxide used is, based on the hydroxyl group and the carboxyl group of the alkylene oxide adduct,
Usually, it is 95 equivalent% or more, preferably 98 to 100 equivalent%. In the above reaction, the monomer can be obtained by heating at room temperature or, if necessary, removing the eliminated alcohol.

The other ethylenically unsaturated monomer (B) is not particularly limited as long as it undergoes addition polymerization, and examples thereof include the following. (A) Vinyl hydrocarbons (a1) Aliphatic vinyl hydrocarbons: ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene, 1,4-pentadiene, 1, 6-
Hexadiene, 1,7-octadiene, α-
Olefins, etc. (a2) Alicyclic vinyl hydrocarbon: cyclohexene,
(Di) cyclopentadiene, pinene, limonene, indene, vinylcyclohexene, ethylidene bicycloheptene, etc. (a3) Aromatic vinyl hydrocarbon: styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, Isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene,
Benzyl styrene, crotyl benzene, vinyl naphthalene, divinyl benzene, divinyl toluene, divinyl xylene, divinyl ketone, trivinyl benzene, etc.

(B) Hydroxyl group-containing vinyl monomers hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol Crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-buten-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, etc

(C) Nitrogen-containing vinyl monomer (c1) Amino group-containing vinyl monomer: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) Acrylamide,
(Meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine,
Crotylamine, N, N-dimethylaminostyrene, methyl α-acetoaminoacrylate, vinylimidazole, N-vinylpyrrole, etc. (c2) Amide group-containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-
Butyl acrylamide, diacetone acrylamide, N
-Methylol (meth) acrylamide, N, N'-methylene-bis (meth) acrylamide, cinnamamide,
N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc.

(D) Epoxy group-containing vinyl monomers glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(E) Halogen element-containing vinyl monomer vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, dichlorostyrene, chloroprene, etc.

(F) vinyl esters, vinyl ethers,
Vinyl ketones Vinyl formate, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate,
Diallyl adipate, isopropenyl acetate, vinyl acylate, vinyl methacrylate, vinyl methoxy acetate, vinyl benzoate, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether,
Vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro-1,2-pyran,
2-butoxy-2'-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl Sulfone, divinyl sulfoxide, dimethyl fumarate, dimethyl maleate, poly (meth) allyloxyalkanes [diaryloxyethane,
Triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc.]

(G) Alkyl (meth) acrylate Alkyl (meth) having an alkyl group having 1 to 50 carbon atoms
Acrylates, for example methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc.

(H) Vinyl monomer having a polyalkylene glycol chain, polyethylene glycol (molecular weight: 300), mono (meth)
Acrylate, polypropylene glycol (molecular weight 50
0) Monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth)
Acrylate, etc.

(I) Poly (meth) acrylates Poly (meth) acrylates of polyhydric (2 to 8) alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.

(J) Other vinyl monomers: acetoxystyrene, methyl 4-vinylbenzoate,
Phenoxystyrene, cyclohexyl methacrylate,
Benzyl methacrylate, ethyl α-ethoxy acrylate, phenyl (meth) acrylate, isocyanatoethyl (meth) acrylate, cyanoacrylate, m-
Isopropenyl-α, α-dimethylmethylbenzyl isocyanate

In (B), preferably, the HLB value is 10
It is the following, more preferably 8 or less, particularly preferably pentaerythritol triacrylate and dipentaerythritol hexaacrylate. The HLB value of the present invention is the HLB of Griffin (“New
Introduction to Surfactants ”(P128 issued by Sanyo Chemical Industries, Ltd.)
Is a value calculated by

In the coating agent of the present invention, the weight ratio of monomer (A) / monomer (B) is 5/95 to 99/1,
Preferably 55/35 to 95/5, more preferably 6
0/40 to 90/10. Curing methods include irradiation with ultraviolet rays, electron beams, and light energy, and curing with heat. When using ultraviolet light, a known sensitizer can be used in combination. The amount of the sensitizer used is monomer (A) and monomer (B)
0.1 to 10% by weight, preferably 1 to 6%, and more preferably 2 to 4%, based on the total weight of In the case of curing by heat, a known polymerization initiator can be used in combination. The amount of the polymerization initiator used is 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the monomers (A) and (B).
%, More preferably 1 to 3%.

Known sensitizers for ultraviolet curing include the following. (A) benzoin ether polymerization initiator benzoin alkyl ether, etc. (b) benzophenone polymerization initiator: benzophenone,
Benzyl, methyl orthobenzoyl benzoate, etc. (c) acetophenone-based polymerization initiator benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4′-isopropyl-
2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone (c) thioxanthone polymerization initiator 2-chlorothioxanthone, 2-methylthioxanthone,
2-isopropylthioxanthone Among the above, a benzoin ether-based polymerization initiator is preferable.

Known polymerization initiators used for curing by heat include the following. (D1) Peroxide polymerization initiator acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, 2,4-dichlorobenzoyl peroxide, t-butylperoxy Vivalate, 3,5,5-
Trimethylhexanyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionitrile peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexa Noate, benzoyl peroxide, parachlorobenzoyl peroxide, t
-Butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, cyclohexanone peroxide, t-butylperoxyisopropylcarbonate, 2,5-dimethyl-2,5-dibenzoylper Oxyhexane, t-butylperoxyacetate, t-butylperoxybenzoate, diisobutyldiperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, t-butyl cumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, pinane hydroperoxide, 2,5- Methyl-2,5-dihydro peroxide, cumene peroxide, etc. (d2) an azo-based polymerization initiator: 2,2'-azobisisobutyronitrile, 1,1'-azo-bis-cyclohexane 1-
Carbonitrile, 2,2'-azobis-4-methoxy-
2,4-dimethylvaleronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, etc. (d3) Non-aqueous redox polymerization initiator Oil-soluble peroxide such as hydroperoxide, dialkyl peroxide, diacyl peroxide And a tertiary amine, naphthenate,
Combined use with oil-soluble reducing agents such as mercaptans and organometallic compounds (triethylaluminum, triethylboron, diethylzinc, etc.) Of these, hydroperoxides or peroxyesters are preferred, and more specifically, di (4- (t-butyl) cyclohexylperoxydicarbonate or cumene hydroperoxide is preferred.

The coating agents of the present invention include unsaturated polyester resins, inorganic fillers, carbon black, dyes and pigments such as titanium oxide, polyethylene glycol (PEG) having a molecular weight of 100 to 600, chelates, fats and oils, surface active agents Agents, bentonite, cellulose, starch, weathering stabilizers and the like can be appropriately compounded. These amounts are not particularly limited, but from the quality of the obtained coating agent,
Usually, it is at most 85% by weight, preferably at most 70% by weight, particularly preferably at most 20% by weight, based on the total weight of (A) and (B).

The coating agent of the present invention is applied to the surface of a substrate, and a cured coating film is formed by irradiation with ultraviolet light, electron beam, light energy, and heat to obtain a coated object. Various inorganic substances (iron, tin, tin,
Aluminum, zinc steel plate, glass, tile slate, ceramic, etc.) and organic matter (rubber (natural rubber, chloroprene rubber, isoprene rubber, neoprene rubber, etc.), plastic (polyolefin such as polyethylene and polypropylene; polystyrene, ABS, vinyl chloride, polycarbonate, Polyacetal, polyester, polyamide, polyurethane, modified PPO, polymethyl methacrylate, epoxy resin, phenol resin, melanin resin, etc.) and the like, and are particularly suitable for polyolefin-based substrates. Further, the amount of application can be variously changed, but is usually 1 to 100 μm.

[0027]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the following, “parts” and “%” are based on weight, respectively.

Production Example 1 448 g of 2-hydroxyethyl acrylate, 204.2 g of aluminum isopropoxide (trade name: AIPD, manufactured by Kawaken Fine Chemicals Co., Ltd.) and 0.06 g of hydroquinone were charged into a 1 L four-necked kolben, and air was blown for 1 m.
Heat to 80 ° C. while blowing into l / liquid separation. 80 ℃
When the temperature reached, 180 g of the isopropyl alcohol desorbed was removed by reducing the pressure inside the Kolben to obtain 472.2 g of a compound (1) having the following structural formula. _{[H 2 C = CH-COO} -C 2 H 4 O] 3 -Al

Production Example 2 480 g of 2-hydroxyethyl methacrylate, 226.8 g of titanium isopropylate (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.06 g of hydroquinone were charged into a 1 L four-necked kolben, and air was blown into the liquid at 1 ml / liquid separation. While heating to 80 ° C. When the temperature reached 80 ° C., 180 g of the isopropyl alcohol desorbed was removed by reducing the pressure in the Kolben to obtain 526.8 g of a monomer (2) having the following structural formula. _{[H 2 C = C (CH} 3) -COO-C 2 H 4 O] 4 -Ti

Example 1 In 60 parts of the compound (1) obtained in Production Example 1, 37 parts of "Neomer DA-600" (dipentaerythritol hexaacrylate; manufactured by Sanyo Chemical Industries) and "Darocur 1173" as a photopolymerization initiator were added. (Made by Ciba Geigy Japan)
3 parts were mixed.

Example 2 37 parts of "Light Ester PE-3A" (pentaerythritol triacrylate; manufactured by Kyoeisha Chemical) and 60 parts of compound (1) obtained in Production Example 1 and "Darocur 1173" as a photopolymerization initiator were added. 3 parts were mixed.

Example 3 In 60 parts of the compound (1) obtained in Production Example 2, 37 parts of "Nomer DA-600" (dipentaerythritol hexaacrylate; manufactured by Sanyo Chemical Industries) and "Darocur 1173" as a photopolymerization initiator were added. 3 parts were mixed.

Example 4 To 60 parts of the compound (1) obtained in Production Example 2, 37 parts of "light ester PE-3A" (pentaerythritol triacrylate; manufactured by Kyoeisha Chemical Co., Ltd.) and "Darocur 1173" as a photopolymerization initiator were added. 3 parts were mixed.

Comparative Example 1 "Neomer DA-600" (dipentaerythritol hexaacrylate; Sanyo Kasei Kogyo) 37 parts and "Polyester PE-3A" (pentaerythritol triacrylate; Kyoeisha Chemical) 60 parts and photopolymerization 3 parts of "Darocur 1173" were mixed as an initiator.

Comparative Example 2 97 parts of "light ester PE-3A" (pentaerythritol triacrylate; manufactured by Kyoeisha Chemical Co., Ltd.) and 3 parts of "Darocur 1173" as a photopolymerization initiator were mixed.

The coating agents of Examples 1 to 4 and Comparative Examples 1 and 2 were applied on a 15-mm-thick PET film so as to have a thickness of 10 mm, and were turned on by a high-pressure mercury lamp of 80 W / cm. 5m at a position 8cm below the lamp
/ Min to obtain a polymerized and cured coating agent. These coating agents were evaluated for pencil hardness, heat resistance and flame retardancy. Table 1 shows the results.

[0037]

[Table 1]

Pencil hardness The pencil was pushed forward at an angle of 45 ° C. under a load of 1 kg to show a state in which no scratches were left. Heat resistance The coating film appearance (visual judgment) after storage at 110 ° C. for 10 hours was judged by “O” and “X”. ：: No coloration, no defects in the coating film. X: Coloring was observed in the coating film. Flame retardancy A flammability test was performed using the oxygen index. The test method conformed to JIS K7201-2.

[0039]

The coating agent obtained according to the present invention exhibits extremely excellent heat resistance and flame retardancy.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 FA011 FA051 FA061 FA111 FA121 FA271 GA01 GA03 GA07 GA08 GA12 JA33 JA66 JB03 JB16 JC02 JC37 JC38 KA03 MA08 MA10 NA14 NA15 PA17 PB09 PC02 PC03 PC07 PC08 4J100 AAQAAQAAQA AB01Q AB02Q AB03Q AB04Q AB07Q AB08Q AB15Q AB16Q AC02Q AC03Q AC04Q AC11Q AD01Q AD03Q AD11Q AE02Q AE03Q AE04Q AE09Q AE26Q AE76P AE77P AF10Q AF11Q AG01Q AG02Q AG03Q AG04Q AG08Q AG15P AG64Q AG70Q AL09Q AL10Q AL66P AL67P AL75Q AL92P AM14Q AM15Q AM17Q AM19Q AM21Q AM24Q AN03Q AN04Q AP01Q AP02Q AQ06Q AQ08Q AQ12Q AQ19Q AR05Q AS06Q AS07Q AT08Q AU21Q BA02P BA03Q BA04Q BA05Q BA08P BA08Q BA10Q BA14Q BA15P BA17P BA29Q BA30Q BA31Q BA42Q BA52Q BA53Q BA55Q BA58Q BA93P BC04Q BC43Q BC53Q BC5401 BC79Q79

Claims (7)

[Claims] 1. A coating agent comprising a metal-containing ethylenically unsaturated monomer (A) represented by the following general formula (1) and another ethylenically unsaturated monomer (B). Embedded image Wherein, M is a divalent to tetravalent metal, R ¹ is a hydrogen atom or a methyl group, m is an integer from 2 to 4, X is ^{-O- (R 2 O) n -} , - C
^{O-O- (R 2 O)} n-, -CO-O- (R 2 O) n-CO-R 3 -CO-O-, -CH 2 O- (R 2 O) n- or -CH ₂ O-CO-R ³ -C
N represents an integer of 1 to 8, R ² represents an alkylene group having 1 to 4 carbon atoms, and R ³ represents an alkylene group having 2 to 4 carbon atoms or 2 to 2 carbon atoms.
4 represents an alkenylene group. ] 2. The coating agent according to claim 1, wherein M in the general formula (1) is an alkaline earth metal, a IIIa metal, an IVa metal or a transition metal. 3. The coating agent according to claim 1, wherein the M content in the general formula (1) is 1% by weight or more. 4. The coating agent according to claim 1, wherein the weight ratio of monomer (A) / monomer (B) is 5/95 to 99/1. 5. The monomer (B) is a vinyl hydrocarbon, a hydroxyl group-containing vinyl monomer, a nitrogen-containing vinyl monomer, an epoxy group-containing vinyl monomer, a halogen element-containing vinyl monomer, a vinyl ester, a vinyl ether, or a vinyl ketone. The coating agent according to any one of claims 1 to 4, wherein the coating agent is selected from the group consisting of a vinyl monomer having an alkyl (meth) acrylate, a poly (meth) acrylate and a polyalkylene glycol chain. 6. The coating agent according to claim 1, wherein the monomer (B) has an HLB value of 10 or less. 7. A coated object having a cured coating film of the coating agent according to claim 1 on the surface of a substrate.