JPH09136981A - Emulsion coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an emulsion coating composition which is lowly polluting and lowly toxic, has excellent storage stability, good water resistance and weather resistance and can form a crosslinked cured film when irradiated with an actinic radiation by mixing specified components with each other. SOLUTION: This emulsion coating composition is prepared by adding 10-900 pts.wt. water to a mixture containing 100 pts.wt. radical-polymerizable monomer or oligomer with 0.1-10 pts.wt. photopolymerization initiator and 2-24 pts.wt. radical-polymerization reactive surfactant. The surfactant is particularly desirably a combination of a polyoxyethylemealkylphenyl ether of formula I (wherein R1 is H or methyl; R2 is a 1-20C alkyl; and (n) is 8-40) with a bis(polyoxyethylene polycyclic phenyl ether) (meth)acrylate sulfate ester salt of formula II (wherein R3 and R6 are each H or a 1-25C alkyl; R4 , R5 , R7 and R8 are each H, a 1-20C alkyl, benzyl or styrene; R9 is H or methyl; (n) is 5-15: and X is an alkali metal or ammonium).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an emulsion coating material composition for forming a crosslinked cured coating on a substrate by irradiation with active energy rays.

[0002]

2. Description of the Prior Art Active energy ray curable resins are used in a wide range of fields because of their good productivity, low temperature curability, low pollution caused by being solventless or low solvent. However, although these resins are solvent-free and low-solvent, when these resins are used as paints, a large amount of solvent is added for the purpose of adjusting viscosity.

In recent years, regulations on volatile organic solvents have been enforced in Europe and the United States, and resin compositions using organic solvents are unavoidably changed to solvent-free or non-solvent type. Since environmental protection based on these regulations is carried out on a global scale, it is inevitable that the regulations will be tightened in Japan soon, and there is a demand for urgent development of alternatives to solvent-based resins. In addition, the use of volatile organic solvents poses a problem due to the large impact on the human body at the present time when improvements in the working environment are being further improved. Solventization and nonsolventization are required.

[0004]

An object of the present invention is to realize a low-pollution and low-toxicity, excellent storage stability, good water resistance and weather resistance, and a crosslinked cured film on a substrate by irradiation with active energy rays. It is to provide an emulsion coating material composition capable of forming.

[0005]

The present invention provides (A) 100 parts by weight of at least one radically polymerizable monomer or oligomer, and (B) 0.1 to 1 of a photopolymerization initiator.
0 parts by weight, (C) radical polymerization reactive surfactant 2 to 2
The emulsion coating material composition is characterized in that (D) 10 to 900 parts by weight of water is added to a mixture containing 4 parts by weight.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the component (A) in the composition of the present invention, a radically polymerizable monomer or oligomer may be used alone or in combination of two or more kinds. The component (A) is a crosslinked cured film. It is the main agent that determines the main performance of. As the component (A), an ester type (meth) acrylate (a-1) obtained by a condensation reaction of an aliphatic, alicyclic or aromatic mono- or polyalcohol with (meth) acrylic acid, in the molecule Urethane poly (meth) acrylate (a-2) obtained by reacting an isocyanate compound having two or more isocyanate groups with a (meth) acrylate having a hydroxyl group or a thiol group, at least two epoxy groups in the molecule An epoxy poly (meth) acrylate (a-3) obtained by a glycidyl group ring-opening reaction of a compound having the formula (meth) acrylic acid, a saturated or unsaturated polyvalent carboxylic acid, a polyhydric alcohol and (meth) acrylic acid Polyester poly (meth) acrylate (a-
4) etc. (meth) acryloyl functional monomers or oligomers, vinyl compounds (a-5) such as styrene, chlorostyrene, bromostyrene, dibromostyrene, divinylbenzene, etc., diethylene glycol bisallyl carbonate, diallyl phthalate diallyl biphenylate, etc. (Meth) allyl compound (a-6) and the like can be mentioned.

Preferred specific examples of (a-1) include aliphatic mono (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, hydroxylethyl (meth) acrylate and hydroxylpropyl (meth) acrylate. Alicyclic mono (meth) acrylates such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, phenyl (meth) acrylate , Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy-2
-Methylethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-
Phenylphenyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 2-phenylphenyl-2-methyloxyethyl (meth) acrylate, 2-naphthyl (meth) acrylate, 2-bromophenyl (meth) acrylate, 4-bromophenyl (meth) acrylate, 2,4-dibromophenyl (meth)
Aromatic mono (meth) acrylates such as acrylate, 2,4,6-tribromophenyl (meth) acrylate, phenylthioethyl (meth) acrylate, phenylthioethoxyethyl (meth) acrylate,

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (n = 4 to 15) di (meth) acrylate, propylene glycol di (meth) acrylate,
Tripropylene glycol di (meth) acrylate, polypropylene glycol (n = 4 to 15) di (meth) acrylate, 1,4-butanediol di (meth) acrylate, polybutylene glycol (n = 2 to 15) di (meth) Acrylate, neopentyl glycol di (meth) acrylate, di (meth) acrylate of hydroxy hivalic acid neopentyl glycol ester, 1,6
-Hexanediol di (meth) acrylate, 1,9-
Aliphatic skeleton ester di (meth) acrylate such as nonanediol di (meth) acrylate, bis (4- (meth) acryloxycyclohexyl) methane, bis (4-
(Meth) acryloxyethoxycyclohexyl) methane, bis (4- (meth) acryloxydiethoxycyclohexyl) methane, bis (4- (meth) acryloxycyclohexyl) propane, bis (4- (meth) acryloxyethoxycyclohexyl) Propane, bis (4-
Alicyclic skeleton ester di (meth) acrylate such as (meth) acryloxydiethoxycyclohexyl) propane and dicyclopentanedi (meth) acrylate;

Bis (4- (meth) acryloxyethoxyphenyl) methane, bis (4- (meth) acryloxydiethoxyphenyl) methane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2, 2
-Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) ) Propane, 2,2-bis (4- (meth) acryloxydipropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxy-3,5-dibromophenyl) propane, 2,2- Bis (4- (meth) acryloxydiethoxy-3,5-dibromophenyl) propane,
2,2-bis (4- (meth) acryloxypentaethoxy-3,5-dibromophenyl) propane, bis (4-
(Meth) acryloxyethoxyphenyl) sulfone,
Bis (4- (meth) acryloxydiethoxyphenyl)
Ester di (meth) acrylates having an aromatic skeleton such as sulfone, bis (4- (meth) acryloylthiophenyl) sulfide, and bis (4- (meth) acryloxyethylthiophenyl) sulfide are listed, and trimethylolpropane is also included. Multifunctional (meth) acrylates such as tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Can be mentioned.

Preferred examples of (a-2) are tris (isocyanatohexyl) isocyanurate, isophorone diisocyanate, bis (4,4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) cyclohexane. , Metaxylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and other polyisocyanate compounds and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Examples thereof include urethane poly (meth) acrylate which is a reaction product with a (meth) acrylate having a hydroxyl group such as butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

Specific preferred examples of (a-3) include:
2,2-bis (4-glycidyloxycyclohexyl)
Propane, 2,2-bis (4-glycidyloxyphenyl) propane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol S diglycidyl ether, etc. An epoxy compound of
Examples thereof include epoxy poly (meth) acrylate which is a reaction product with (meth) acrylic acid.

Specific preferred examples of (a-4) include at least one of maleic acid, fumaric acid, phthalic acid, or succinic acid and ethylene glycol, propylene glycol, butylene glycol, trimethylolpropane,
Alternatively, at least one polyhydric alcohol such as pentaerythritol and polyester poly (meth) acrylate, which is a reaction product with (meth) acrylic acid, may be used.

Examples of the photopolymerization initiator as the component (B) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal and 2,2-diethoxy. Acetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, ethylphenyl glyoxylate, 2-hydroxy-2-
Carbonyl compounds such as methyl-1-phenylpropan-1-one, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, 2,
Examples thereof include 4,6-trimethylbenzoyldiphenylphosphine oxide and acylphosphine oxide such as CGI-100.

The component (B) is added in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the component (A). When the compounding amount of the component (B) is less than 0.1 part by weight, the curability is insufficient, and when it exceeds 10 parts by weight, the cured coating is colored.

The radical polymerization reactive surfactant as the component (C) is an essential component for obtaining a uniform emulsion. Such radical polymerization-reactive surfactants are those having a radical-reactive unsaturated bond in the molecule, and specifically include acrylic, allyl-based, maleic acid-based and itaconic acid-based surfactants. To be

Specific examples of the component (C) include polyoxyethylene lauryl ether maleic acid ester, polyoxyethylene lauryl ether methacrylic acid ester,
Polyoxyethylene nonylphenyl ether acrylic acid ester, allyl group-containing polyoxyethylene nonylphenyl ether, polyoxyethylene alkylphenyl ether represented by general formula [I], sulfoethyl methacrylate sodium salt, sulfoethyl methacrylate ammonium salt, allyl group Containing polyoxyethylene nonyl phenyl ether sulfonate, bis (polyoxyethylene polycyclic phenyl ether) represented by the general formula [II]
Examples thereof include (meth) acrylated sulfate ester salts.

Among them, from the viewpoint of high emulsifying ability for radically polymerizable monomers or oligomers and good emulsion stability, the above general formula [I] is used.
The polyoxyethylene alkyl phenyl ether (C-1) represented by the formula (1) and the bis (polyoxyethylene polycyclic phenyl ether) (meth) acrylated sulfate ester salt (C-2) represented by the general formula [II] are used in combination. Is particularly preferred.

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
The alkyl group of 20 and m show the integer of 8-40. )

Embedded image (In the formula, R ₃ and R ₆ are a hydrogen atom or an alkyl group having 1 to 25 carbon atoms and may be the same or different,
R ₄ , R ₅ , R ₇ , and R ₈ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a benzyl group, or a styrene group, which may be the same or different, and R ₉ is a hydrogen atom or methyl. Indicates a group. n is an integer of 5 to 15, and X is an alkali metal atom or ammonium. )

Specific examples of (C-1) include polyoxyethylene nonylphenyl ether methacrylate, and specific examples of (C-2) include esters of nonylphenol-formaldehyde condensate obtained by addition polymerization of 10 mol of ethylene oxide. Examples thereof include ammonium sulfate salt and ester sulfate sodium salt of styrenated octylphenol formaldehyde condensate obtained by addition polymerization of 8 mol of ethylene oxide. The component (C) can be used alone or in a mixture of two or more.

The proportion of component (C) used is 10 parts of component (A).
2 to 24 parts by weight with respect to 0 parts by weight, more preferably 4 to
16 parts by weight. If the amount of the component (C) blended is less than 2 parts by weight, a stable emulsion cannot be obtained.
When it exceeds the weight part, water resistance and weather resistance are poor, and the adhesion of the cured film is poor.

The water as the component (D) is added for the purpose of lowering the viscosity of the composition comprising the components (A) to (C) and facilitating the coating. The water as the component (D) is 10 to 900 parts by weight, preferably 40 to 3 parts by weight, relative to 100 parts by weight of the component (A).
It is compounded in an amount of 00 parts by weight. If the blending amount is less than 10 parts by weight, the viscosity is too high and the coating is difficult.
If it exceeds the weight part, it cannot be applied uniformly on the substrate, and a smooth continuous film cannot be obtained.

The emulsion coating material composition of the present invention comprises:
If necessary, additives such as an antioxidant, an anti-yellowing agent, a bluing agent, a pigment, a leveling agent, an antifoaming agent, a thickener, an anti-settling agent and the like may be added.

In order to obtain the emulsion coating composition of the present invention, a method using a blend comprising components (A) to (D) using a high speed disperser, a double cylinder homogenizer, an ultrasonic homogenizer, a blender, a mixer, or the like, An emulsion is obtained by emulsifying by a method such as film emulsification.

The emulsion coating composition of the present invention can be applied to a substrate by brush coating, spray coating, dip coating, spin coating, curtain coating, etc., but the coating workability, the smoothness of the coating, and the uniform coating are obtained. From the viewpoints of properties, adhesion to a substrate, etc., the coating material composition is appropriately adjusted to a viscosity suitable for each coating method, and the coating composition is applied by a method according to the shape of the substrate. In coating the base material, it is preferable to heat the base material in order to form a uniform coating film on the base material and to quickly dry the base material. The heating of the base material is performed by emulsion coating. Further improves the adhesiveness of the material composition. The emulsion coating material composition is applied onto a substrate so that the cured film thickness is 1 to 50 μm, preferably 3 to 20 μm. When the film thickness is out of this range, physical properties of the cured film such as cracks occurring in the cured film due to curing shrinkage are not sufficiently exhibited.

The emulsion coating composition of the present invention is applied to a substrate and then crosslinked by irradiation with active energy rays such as ultraviolet rays and electron beams to form a cured coating film. Curing by irradiation with active energy rays uses, for example, a high pressure mercury lamp, a metal halide lamp or the like, and a wavelength of 10
UV light of 0-400nm 1000-5000mJ
Irradiation is performed so that it becomes / cm ² . The atmosphere for the active energy ray irradiation may be air or an inert gas such as nitrogen or argon.

The base material to which the emulsion coating composition of the present invention is applied includes various base materials such as synthetic resin, metal, wood and paper, and the purpose of application is also waterproof, scratchproof and rustproof. ,
It can be used for various purposes such as surface protection such as antifouling and antiseptic, imparting functionality such as antistatic and antifogging, and improving appearance such as coloring, polishing and matting.

[0026]

The present invention will be described below in more detail with reference to examples. In the examples, “parts” means “parts by weight”.
The evaluation items were evaluated according to the following method.

(1) Emulsion stability 100 ml of the emulsion immediately after re-emulsification was put in a test tube with a scale, and the emulsified state and the visual appearance were evaluated. ◎: No separation even after 3 months ○: Even if slightly separated, it can be easily restored to an emulsified state by mixing with hands ×: Separated within 3 months and cannot be re-emulsified even if mixed by hand XX: Those that are separated into two layers without being re-emulsified

(2) Appearance of cured film The appearance of the film after curing the composition was visually evaluated. A cured film having a smooth surface and no defects such as pinholes and cissing was regarded as good, and other than that, problems in appearance were described.

(3) Initial Adhesion Cross-cut was applied to the cured film at intervals of 1 mm to reach the base material, 100 100 squares of 1 mm ² were made, and cellophane tape was adhered on top of it to rapidly peel it off, but it did not peel off. I counted the number of crosses. ○: No peeling △: 1 to 25 peeled ×: 26 peeled or more (4) Water resistance A coated plate sample coated with the coating material composition was heated in a water bath at 80 ° C for 2 hours, and the appearance and cracks of the cured film were observed. Was visually observed to test the adhesion. -Adhesion: According to the evaluation of (3) above.

(5) Weather resistance A sunshine carbon weather ometer (manufactured by Suga Test Instruments Co., Ltd., WEL-SUN-HC-B type) using a weather resistance tester, a black panel temperature of 63 ± 3 ° C., irradiation rainfall for 12 minutes,
A 48 minute irradiation cycle was tested for 1000 hours.・ Appearance evaluation: △ YI value (△ YI =
YI (after weathering test) -YI (initial) was measured. ◯: 0 ≦ ΔYI <1 Δ: 1 ≦ ΔYI <3 ×: 3 ≦ ΔYI ・ Crack: According to the evaluation of (4) above. -Adhesion: According to the evaluation of (3) above.

(Environmental Contamination) In the film forming process, those that did not generate a solvent were marked with ◯, and those with a solvent were marked with x.

[0032]

【Example】

[Examples 1 to 4 and Comparative Examples 1 to 5] The coating material compositions were prepared at the compounding ratios shown in Table 1 using an ultrasonic homogenizer.
This composition was preliminarily heated in a dryer at 80 ° C. for 30 minutes and had a thickness of 3 mm polymethylmethacrylate resin plate (Mitsubishi Rayon Co., Ltd .; trade name: Acrypet VH).
Was spray-coated so that the cured film had a thickness of 10 μm. After evaporating the water content by heating, a high-pressure mercury lamp was used in the air to irradiate with ultraviolet rays having a wavelength of 340 to 380 nm and an integrated light amount of 1000 mJ / cm ² , to obtain a cured film. The evaluation results of the obtained coating film are shown in Tables 1 and 2.

Example 5 A coating material composition having the compounding ratio shown in Table 1 was prepared using an ultrasonic homogenizer. This composition was preliminarily heated at 80 ° C. for 30 minutes in a drier, and a polycarbonate resin plate (manufactured by GE; trade name: Lexan LS-II) having a thickness of 3 mm was coated so that the cured film had a thickness of 25 μm. I did a dip coat. After evaporating the water content by heating, use a high pressure mercury lamp in air to
A cured coating film was obtained by irradiating with ultraviolet rays having an integrated light amount of ˜380 nm of 1500 mJ / cm ² . Table 1 shows the evaluation results of the obtained coatings.

Example 6 A coating material composition was prepared by using an ultrasonic homogenizer with the components and compounding ratios shown in Table 1. This composition was spray-coated on a steel plate having a thickness of 1 mm (surface-treated with zinc phosphate) which had been heated in a dryer for 30 minutes in advance so that the cured film had a thickness of 8 μm.
After evaporating the water content by heating, a high pressure mercury lamp was used in the air, and the accumulated light amount at a wavelength of 340 to 380 nm was 10
Ultraviolet rays of 00 mJ / cm ² were irradiated to obtain a cured film.
Table 1 shows the evaluation results of the obtained coatings.

[Comparative Example 6] A coating material composition having the components and compounding ratios shown in Table 2 was mixed as a solvent with isobutanol / normal butyl acetate / butyl cellosolve / cellosolve acetate in a ratio of 140/50/20/10. 3 mm thick polycarbonate resin plate (manufactured by GE; product name: dissolved in a solvent and preliminarily heated at 80 ° C. for 30 minutes in a dryer)
Lexan LS-II) was spray-coated so that the cured film had a thickness of 8 μm. After volatilizing the solvent by heating, in the air, using a high pressure mercury lamp, a wavelength of 340 to 3
Ultraviolet rays having an integrated light amount of 80 nm and 1000 mJ / cm ² were irradiated to obtain a cured film. Table 1 shows the evaluation results of the obtained coatings.

[0036]

[Table 1]

[0037]

[Table 2]

The symbols in Tables 1 and 2 have the following meanings. HX-2: 1,6-hexanediol diacrylate TMPTA: trimethylolpropane triacrylate PE4A: pentaerythritol tetraacrylate DPHA: dipentaerythritol hexaacrylate TAIC: manufactured by Hitachi Chemical Co., Ltd., trade name: Funkryl
FA-731A M6400: manufactured by Toa Synthetic Chemical Industry Co., Ltd., trade name: Aronix M-6400 oligoester acrylate M8030: manufactured by Toa Synthetic Chemical Industry Co., Ltd., trade name: Aronix M-8030 oligoester acrylate BNP: benzophenone MS60: Bis (polyoxyethylene triphenyl ether) methacrylated ammonium sulfate salt (Nippon Emulsifier Co., Ltd., trade name: Antox MS-60) RMA-506: Polyoxyethylene nonylphenyl ether acrylate (Nippon Emulsifier Co., Ltd., RMA- 5
06) EM5: polyoxyethylene nonyl phenyl ether
EO addition 5 mol STC: stearyl trimethyl ammonium chloride BTMS: bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate HBPB: 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole Acrylic: Polymethylmethacrylate resin Polycarbonate: Polycarbonate resin

The emulsion coating material composition of the present invention comprises
Since it does not require the use of a solvent, it is a low-pollution, low-toxicity coating material composition that does not have an adverse effect on the environment, and is also highly solid with excellent water resistance, weather resistance, and storage stability. The coating composition has good coatability even by minute, and a good crosslinked cured coating can be formed on a substrate by irradiation with active energy rays.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C09D 5/02 PPT

Claims (2)

[Claims] 1. To (A) 100 parts by weight of at least one radically polymerizable monomer or oligomer,
10 to 900 parts by weight of (D) water is added to a mixture containing 0.1 to 10 parts by weight of a photopolymerization initiator (B) and 2 to 24 parts by weight of a radical polymerization reactive surfactant (C). The emulsion coating material composition. 2. A polyoxyethylene alkylphenyl ether (meth) acrylate represented by the general formula (I) as the component (C) and a bis (polyoxyethylene polycyclic phenyl ether) represented by the general formula (II) ( The emulsion coating material composition according to claim 1, further comprising a (meth) acrylated sulfuric acid ester salt. Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
The alkyl group of 20 and m show the integer of 8-40. ) (In the formula, R ₃ and R ₆ are a hydrogen atom or an alkyl group having 1 to 25 carbon atoms and may be the same or different,
R ₄ , R ₅ , R ₇ , and R ₈ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a benzyl group, or a styrene group, which may be the same or different, and R ₉ is a hydrogen atom or methyl. Indicates a group. n is an integer of 5 to 15, and X is an alkali metal atom or ammonium. )