JP5450922B2 - Surface modifier for active energy ray-cured film-forming composition - Google Patents

Description

  The present invention relates to a surface conditioner such as a leveling agent or an antifoaming agent that is added to a composition that forms a film by curing with active energy rays and is used to improve the physical properties of the film surface. is there.

  Some film forming compositions such as paints and coating agents for coating a base material are polymerized by an active energy ray such as ultraviolet rays and cured to form a film.

  In particular, the solvent-free film-forming composition has features that there is no fear of environmental pollution due to volatilization of the solvent, and that it contributes to energy saving because it is polymerized and cured efficiently and quickly by irradiation with active energy rays for a short time. On the other hand, since this film-forming composition is solvent-free and has high viscosity and hardens rapidly, bubbles that could not be degassed remain in the film, or foam marks and spots appear on the surface of the film. In addition, the thickness of the coating is non-uniform, and the smoothness and uniformity of the coating cannot be maintained. Therefore, a surface conditioner such as a leveling agent (also referred to as a smoothing agent) or an antifoaming agent made of a (meth) acrylic acid ester polymer, a vinyl ether polymer, or a modified silicone oil in advance. Is added.

  Patent Document 1 discloses a polymer solution composed of a (meth) acrylate monomer and a high-boiling alcohol as a leveling agent added to a paint in order to improve the fluidity of a two-component polyurethane paint or an epoxy paint. ing.

  Patent Document 2 discloses a copolymer of a dibasic acid ester having a polymerizable unsaturated double bond such as maleic acid diester and a (meth) acrylic acid ester monomer as a smoothing agent for an ultraviolet curable coating. ing.

  A film-forming composition having such a surface conditioner is generally excellent in smoothness and antifoaming properties. However, when the film obtained by curing it is wiped with a cloth impregnated with a volatile oil such as an organic solvent or immersed in warm water, whitening may occur.

  On the other hand, Patent Document 3 discloses polyether-modified silicone oil, polyester-modified silicone oil, and perfluoro-modified silicone oil as leveling agents contained in the resin composition for hard coat.

  A film-forming composition having a modified silicone oil is generally excellent in leveling properties. However, the cured film may cause repelling when overcoating or decomposition of silicone during baking.

  In recent years, a cured coating for coating a base material is required to have high added value having various characteristics as well as providing a beautiful appearance and imparting scratch resistance.

Japanese Examined Patent Publication No. 04-40391 JP 2006-56952 A JP 2006-63244 A

  The present invention has been made in order to solve the above-mentioned problems, and imparts sufficient antifoaming property or smoothness to a composition that forms a film by curing with various active energy rays such as ultraviolet rays. An object of the present invention is to provide a surface conditioner to be added to a film-forming composition so as not to deteriorate properties such as volatile oil resistance and water resistance in the cured film.

Active energy ray curable film-forming composition according to claim 1 in the range of made the claims in order to achieve the object of the main chain and addition copolymerization, (meth) at least one acryloyl group and an alkenyl group type of surface adjusting agent antifoaming agent comprising a non-volatile components copolymer is containing chromatic having a side chain containing an unsaturated group, and an active energy ray curable film-forming component of the solvent-free while containing, Active energy that is cured by active energy rays in the absence of solvent when the non-volatile component in the surface conditioning agent is set to 30% as a solid content and the non-volatile component is 0.02 to 1% by weight with respect to the film-forming component. A wire curable film forming composition comprising:
The copolymer is, while the weight average molecular weight of that and 2,000-100,000, is intended to the iodine value and 3-100,
The copolymer forms the main chain by the addition copolymerization of a (meth) acrylic acid derivative having a reactive functional group and an unsaturated aliphatic group-containing derivative not having a reactive functional group. A copolymer that forms the side chain by reaction of a compound having a binding functional group that reacts with and binds to the reactive functional group that the unsaturated functional group has, and the reactive functional group. (Meth) acrylic acid derivatives having a group are converted into 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-methacryloyloxyethyl-2-hydroxyl Pyrphthalate, caprolactone added to 2-hydroxyethyl (meth) acrylate (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, isocyanatoalkyl ( Compound in which isocyanate group of meth) acrylate is blocked with methyl ethyl ketoxime, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl glycidyl ether acrylate, (meth) acrylic acid, 2- (Meth) acryloyloxyethyl succinic acid or 2-methacryloyloxyethyl hexahydrophthalic acid, and the unsaturated aliphatic group-containing derivative having no reactive functional group is methyl (meth) acrylate Ethyl (meth) acrylate, normal propyl (meth) acrylate, isopropyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, normal octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) ) Acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methoxy Ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-octoxyethyl (meta Acrylate, 2-lauroxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, (meth) acrylic acid methoxypolyethylene glycol ester, ( (Meth) acrylic acid methoxypolypropylene glycol ester, (meth) acrylic acid methoxypoly (ethylene-propylene) glycol ester, (meth) acrylic acid methoxypoly (ethylene-tetramethylene) glycol ester, (meth) acrylic acid butoxypoly (ethylene-propylene) glycol Ester, (Meth) acrylic acid octoxypoly (ethylene-propylene) glycol ester, (Meth) acrylic acid lauroxypolyethylene glycol ester, (Meth) Lauroxy poly (ethylene-propylene) glycol acrylate, acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, acroylmorpholine, styrene, α-methylstyrene, chlorostyrene , Vinyl toluene, vinyl acetate, vinyl propionate, methyl vinyl ether, ethyl vinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, tertiary butyl vinyl ether, normal octyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether , Stearyl vinyl ether, salt A compound having vinyl, vinylidene chloride, chloroprene, propylene, butadiene, or isoprene and having the binding functional group and the unsaturated group is represented by 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone (Meth) acrylate added to 2-hydroxyethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, glycidyl (Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl glycidyl ether acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, or 2-methacryloyloxy Ethyl hexahydrophthalic acid,
Or
The copolymer forms the main chain by the addition copolymerization of unsaturated aliphatic groups of an unsaturated aliphatic group-containing derivative having a (meth) acryloyl group and another unsaturated aliphatic group-containing derivative. The unsaturated aliphatic group-containing derivative having a (meth) acryloyl group is 2- (2-vinyloxyethoxy) ethyl acrylate or 2- (2-vinyloxyethoxy) ethyl methacrylate. The other unsaturated aliphatic group-containing derivative is styrene, α-methylstyrene, chlorostyrene, vinyl toluene, vinyl acetate, vinyl propionate, methyl vinyl ether, ethyl vinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, Isobutyl vinyl ether, tertiary butyl vinyl Ether, normal octyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, or diallyl phthalate .

Active energy ray curable film-forming composition according to claim 2, which has been described in claim 1, wherein the copolymer, wherein the random copolymer Karadadea Rukoto.

Active energy ray curable film-forming composition according to claim 3 has been described in claim 1, wherein the copolymer is that having a said reactive functional group and (meth) acrylic acid derivatives, wherein by the said unsaturated aliphatic group-containing derivatives having no reactive functional group be the addition copolymerization, after forming the main chain, a compound having said unsaturated group to the binding functional group reactive Thus, the binding functional group reacts with and binds to the reactive functional group, thereby forming the side chain.

The active energy ray-curable film forming composition according to claim 4 is the composition according to claim 1 , wherein the copolymer has the unsaturated aliphatic group-containing derivative having the (meth) acryloyl group, and said another unsaturated aliphatic group-containing derivative, the by addition copolymerization, by reacting those unsaturated aliphatic groups to each other, characterized in that it is formed by the step of forming the main chain .

The active energy ray-curable film forming composition according to claim 5 is the composition according to any one of claims 1 to 4, wherein the iodine value of the copolymer is 6 to 50. .

The active energy ray-curable film-forming composition according to claim 6 is the composition according to any one of claims 1 to 5 , wherein the active energy ray-curable film-forming component is an epoxy acrylate resin-forming component, urethane resin-forming component is an acrylate, wherein the resin-forming component is a polyester acrylate, and any der Rukoto selected from a resin-forming component is a blend of urethane acrylate and trimethylolpropane triacrylate.

The cured film according to claim 7 is a film obtained by applying the active energy ray-cured film-forming composition according to claim 1 on a substrate, and an active energy selected from ultraviolet rays, infrared rays, far infrared rays, electron beams, and radiation. It is characterized by being cured by irradiation with a line.

  The surface conditioner of the present invention imparts sufficient antifoaming property or smoothness to a composition that forms a film by curing with active energy rays such as ultraviolet rays, only by adding a small amount.

  The active energy ray-cured film-forming composition containing this surface conditioner is rapidly cured with active energy rays in the absence of a solvent to form a film on the substrate.

  The coating is excellent in volatile oil resistance, water resistance and the like.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

  The surface conditioner for the active energy ray curable film-forming composition of the present invention is a radical polymerizable that is a copolymerized main chain and at least one of a (meth) acryloyl group and an alkenyl group that designates an acryloyl group or a methacryloyl group. It contains a copolymer having a branched side chain having an unsaturated group.

  This copolymer has a weight average molecular weight of, for example, 2,000 to 100,000 by gel permeation chromatography. The weight average molecular weight is more preferably 4,000 to 50,000.

  This copolymer has an iodine value, that is, a value obtained by converting the amount of halogen bonded when the halogen is reacted to 100 g of the solid content of the copolymer to 3-100 of iodine. preferable. The iodine value is measured according to JIS K0070. This iodine value is more preferably 6-50.

  If the weight average molecular weight or iodine value of the copolymer is out of the above range, the basic properties such as smoothness and antifoaming properties as a surface conditioner, and an active energy ray curable film forming composition containing the same It becomes difficult to maintain both necessary and sufficient properties such as volatile oil resistance and water resistance of a film obtained by curing an object.

  The copolymer may have an addition copolymerized main chain and a side chain having an unsaturated group that undergoes radical polymerization upon irradiation with active energy rays such as ultraviolet rays, infrared rays, far infrared rays, electron beams, and radiation. is important. The unsaturated group of the side chain in the copolymer may be a (meth) acryl group only, an alkenyl group only, or both. Of these, an acrylic group is preferred.

  This copolymer may be produced by any method. The repeating unit of the copolymer and the ratio thereof are not particularly limited.

  The preferable example of the manufacturing method of a copolymer is shown.

  The first example of the method for producing the copolymer is as follows. First, 1 to 80 molar equivalents of a (meth) acrylic acid derivative having a hydroxyl group, an isocyanate group, a blocked isocyanate group, an epoxy group or a carboxyl group as a reactive functional group, and another reactive group that does not have such a reactive functional group A polymer which is a copolymerization intermediate having a main chain formed by addition copolymerization with an unsaturated aliphatic group-containing derivative of 20 to 99 molar equivalents is obtained. Next, the unsaturated group is formed in the side chain by reaction with a compound having a binding functional group that reacts and bonds to the reactive functional group remaining in the main chain and a radical polymerizable unsaturated group. The obtained copolymer is obtained.

As a (meth) acrylic acid derivative having a reactive functional group,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxy Ethyl-phthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, (meth) acrylate in which 1 to 10 mol of caprolactone is added to 2-hydroxyethyl (meth) acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name) : (Meth) acrylic acid derivatives having a hydroxyl group such as: Plaxel F series;
2-isocyanatoethyl (meth) acrylate (manufactured by Showa Denko KK, trade name: Karenz MOI, Karenz AOI), 1,1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz) (Meth) acrylic acid derivatives having isocyanate groups such as BEI);
(Meth) acrylic acid derivatives having a blocked isocyanate group such as a compound obtained by blocking an isocyanate group of an isocyanatoalkyl (meth) acrylate with, for example, methyl ethyl ketoxime;
(Meth) acrylic acid derivatives having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl glycidyl ether acrylate (product name: 4HBAGE, manufactured by Nippon Kasei Co., Ltd.) ;
Examples include (meth) acrylic acid derivatives having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid.

As an unsaturated aliphatic group-containing derivative having no reactive functional group,
Methyl (meth) acrylate, ethyl (meth) acrylate, normal propyl (meth) acrylate, isopropyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, normal octyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, -Octoxyethyl (meth) acrylate, 2-lauroxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, (meth) acrylic Acid methoxypolyethylene glycol ester [for example, ethylene glycol repeating unit number (r) is 1 to 50], (meth) acrylic acid methoxypolypropylene glycol ester [for example, propylene glycol repeating unit number (r) is 1 to 50 Meth) acrylic acid methoxy poly (ethylene-propylene) glycol ester [for example, those having a total (r) of 2 to 50 ethylene glycol repeating units and propylene glycol repeating units], (meth) Metoki acrylate Poly (ethylene-tetramethylene) glycol ester [for example, those having a total (r) of 2 to 50 ethylene glycol repeating units and tetramethylene glycol repeating units), butoxypoly (meth) acrylate (ethylene-propylene) ) Glycol esters [for example, those having a total (r) of 2 to 50 ethylene glycol repeating units and propylene glycol repeating units], (meth) acrylic acid octoxypoly (ethylene-propylene) glycol esters [for example, ethylene The total (r) of the number of glycol repeating units and the number of propylene glycol repeating units is 2 to 50], (meth) acrylic acid lauroxypolyethylene glycol ester [for example, the number of ethylene glycol repeating units (r) is 2 ~ 50 things], (Me T) Acrylic acid lauroxy poly (ethylene-propylene) glycol ester [for example, having a total number (r) of 2 to 50 ethylene glycol repeating units and propylene glycol repeating units], trifluoroethyl (meth) acrylate, Such as 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,4,4,4, -hexafluorobutyl (meth) acrylate, perfluorooctylethyl (meth) acrylate (meta ) Acrylates;
Acrylamides such as acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, acroylmorpholine;
Aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene and the like;
Vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, tertiary butyl vinyl ether, normal octyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether;
Other vinyl compounds such as vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide and the like can be mentioned.

  There are various other monomers, but the number of monomers used is not limited as long as they can be polymerized and the physical properties of the surface modifier are not impaired.

  As a compound having a binding functional group and a radical polymerizable unsaturated group, when the reactive functional group in the reactive functional group-containing (meth) acrylic acid derivative is a hydroxyl group, the binding functional group is an isocyanate group or Carboxy group or epoxy group, also binding functionality when reactive functional group is isocyanate group, blocked isocyanate group or epoxy group, binding functional group is hydroxyl group or carboxyl group, also binding functionality when reactive functional group is carboxyl group The functional group is an epoxy group, a hydroxyl group, or an isocyanate group, and the unsaturated group is a (meth) acryloyl group or an alkenyl group.

Specifically, as a compound having a binding functional group and a radical polymerizable unsaturated group,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxy Ethyl-phthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, (meth) acrylate in which 1 to 10 mol of caprolactone is added to 2-hydroxyethyl (meth) acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name) : Plaxel F series), compounds having a hydroxyl group and an unsaturated group such as allyl alcohol;
2-isocyanatoethyl (meth) acrylate (manufactured by Showa Denko KK, trade name: Karenz MOI, Karenz AOI), 1,1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz) Compounds having an isocyanate group and an unsaturated group, such as BEI);
Compounds having an epoxy group and an unsaturated group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl glycidyl ether acrylate (trade name: 4HBAGE, manufactured by Nippon Kasei Co., Ltd.);
Examples thereof include compounds having a carboxyl group and an unsaturated group such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid.

  More specifically, description will be made with reference to the following chemical reaction formula (1).

  First, radical addition copolymerization of 2-hydroxyethyl (meth) acrylate, which is a (meth) acrylic acid derivative having a reactive functional group, and ethyl acrylate, which is another (meth) acrylic acid derivative not having the functional group. Let Next, when 2-isocyanatoethyl acrylate is reacted with a hydroxyl group that is a reactive functional group remaining in the main chain, a desired copolymer is obtained. In addition, m and n of the copolymer in the chemical reaction formula (1) are arbitrary numbers satisfying the weight average molecular weight, and the copolymer is a random copolymer or a block copolymer. Also good.

  The 2nd example of the manufacturing method of a copolymer is as follows. Unsaturation of 1 to 80 molar equivalents of an unsaturated aliphatic group-containing derivative having a (meth) acryloyl group and 20 to 99 molar equivalents of another unsaturated aliphatic group-containing derivative not containing a (meth) acryloyl group It can be obtained while controlling gelation by addition copolymerization of aliphatic groups by cationic polymerization.

  Examples of the unsaturated aliphatic group-containing derivative having a (meth) acryloyl group include VEEA (made by Nippon Shokubai Co., Ltd .; trade name), 2- (2-vinyloxy) which is 2- (2-vinyloxyethoxy) ethyl acrylate. VEEM (manufactured by Nippon Shokubai Co., Ltd .; trade name), which is ethoxy) ethyl methacrylate.

As an unsaturated aliphatic group-containing derivative that does not contain a (meth) acryloyl group,
For example, aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene;
Vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, tertiary butyl vinyl ether, normal octyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether ;
Vinyl chloride, vinylidene chloride, chloroprene;
Propylene, butadiene, isoprene;
Fluoroolefin maleimide;
Examples include allyl compounds such as diallyl phthalate.

  Another example will be described more specifically with reference to the following chemical reaction formula (2).

  When 2- (2-vinyloxyethoxy) ethyl acrylate, which is an unsaturated aliphatic group-containing derivative having a (meth) acryloyl group, and isobutyl vinyl ether are subjected to addition copolymerization by cationic polymerization, a desired copolymer is obtained. can get. In addition, p and q of the copolymer in the chemical reaction formula (2) are arbitrary numbers satisfying the weight average molecular weight, and the copolymer is a random copolymer even if it is a block copolymer. Also good.

  The active energy ray-cured film-forming composition is composed of, for example, a resin component such as epoxy acrylate, urethane acrylate, or polyester acrylate, a photopolymerization initiator that generates radicals or cations upon irradiation with active energy rays, and heat as necessary. It is a composition for forming a cured film, which contains a thermal initiator that generates radicals.

  Examples of photopolymerization initiators include only typical ones, benzoin or its derivatives, benzophenone or its derivatives, acetophenone or its derivatives, Michler's ketone, benzyl or its derivatives, tetraalkylthiuram monosulfide, thioxan Compounds that generate radicals of the type, and compounds that generate cationic species of triphenylsulfonium hexafluorophosphonate salt, triphenylsulfonium hexafluoroantimonate salt, diphenyliodohexafluorophosphonate salt, It is not limited to this. As for the compounding quantity of a photoinitiator, about 0.5-10 mass% is preferable in a cured film formation composition.

  As the thermal initiator, known ones can be used, and various peroxides and various azos can be used.

  This surface conditioner imparts defoaming or smoothness to the film forming component other than the volatile component only by adding a small amount of the non-volatile component of the surface conditioner of about 0.02 to 1% by weight. It gives properties such as volatile oil resistance and water resistance to the cured film.

  The composition is applied or sprayed onto a substrate and irradiated with active energy rays such as ultraviolet rays, infrared rays, far infrared rays, electron beams, radiations, etc., to thereby remove unsaturated groups in the side chain in the copolymer. When cross-linked, a coating that is smooth and free from foam traces and spots and has excellent resistance to volatile oil, water resistance and the like is formed.

  The following is an example in which a leveling agent is prototyped as a surface conditioner for an active energy ray curable film forming composition, an active energy ray curable film forming composition containing the same is prepared, and then cured to form a film. Show.

  In addition, all the weight average molecular weights of a copolymer are the values measured using the gel permeation chromatography (GPC) analyzer (Shodex GPC system by Showa Denko KK).

  First, the manufacture example of the leveling agent which is the surface conditioning agent of this invention is shown below.

(Production Example 1 of leveling agent)
In a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, 100 parts by weight of xylene was charged, and the temperature was raised to 115 ° C. while introducing nitrogen gas. Thereto, 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of 2-hydroxyethyl acrylate, 100 parts by weight of xylene, 9 parts by weight of tert-butylperoxy-2-ethylhexanoate The dropping solution (a-1) in which the parts were mixed was dropped at a constant rate over 2 hours with a dropping funnel. After completion of the dropwise addition, the mixture was reacted for 4 hours while maintaining a temperature of 115 ° C. to obtain a polymer. After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or lower, 20 parts by weight of 2-isocyanatoethyl acrylate and 0.05 part by weight of methoquinone as a polymerization inhibitor were added, and reacted at 80 ° C. for 5 hours. It was confirmed that an isocyanate group peak of 2270 cm ⁻¹ disappeared by infrared absorption spectrum measurement (IR). The solid content was adjusted to 30% by dilution with xylene to produce a copolymer xylene solution (A-1). The weight average molecular weight of this copolymer was 8,000. The iodine value of the solid content was 11.

(Production Example 2 of leveling agent)
Instead of the dropping solution (a-1) in the production of the copolymer (A-1) in Production Example 1, 170 parts by weight of ethyl acrylate, 100 parts by weight of 2-ethylhexyl acrylate, 30 parts of methacrylic acid The copolymer (A-1) was used except that a dropping solution (a-2) in which 100 parts by weight of xylene, 100 parts by weight of xylene and 9 parts by weight of tert-butylperoxy-2-ethylhexanoate were mixed was used. ) To give a polymer by the same method as in the production example. After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or less, 44 parts by weight of glycidyl methacrylate, 1 part by weight of triethylamine as a catalyst, and 0.05 part by weight of methoquinone as a polymerization inhibitor were added and reacted at 80 ° C. for 7 hours. The acid value was 4.0 mg · KOH / g, confirming the completion of the reaction. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (A-2). The copolymer had a weight average molecular weight of 10,000. The iodine value of the solid content was 22.

(Production Example 3 of leveling agent)
Instead of the dropping solution (a-1) in the production of the copolymer (A-1) in Production Example 1, 100 parts by weight of ethyl acrylate, 100 parts by weight of normal butyl acrylate, Plaxel FA5 (Daicel Chemical) 100 parts by weight of hydroxyl group-containing acrylate in which 5 moles of caprolactone is added to 2-hydroxyethyl acrylate, 50 parts by weight of xylene, and 4 parts by weight of tert-butylperoxy-2-ethylhexanoate A polymer was obtained by the same method as in Production Example of Copolymer (A-1) except that the dripped solution (a-3) was used. After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or lower, 20 parts by weight of 2-isocyanatoethyl methacrylate and 0.05 part by weight of methoquinone as a polymerization inhibitor were added, and reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (A-3). The weight average molecular weight of this copolymer was 42,000. The iodine value of the solid content was 10.

(Production Example 4 for leveling agent)
Instead of the dropping solution (a-1) in the production of the copolymer (A-1) in Production Example 1, 50 parts by weight of isobutyl acrylate, 200 parts by weight of normal butyl acrylate, 4-hydroxybutyl acrylate A copolymer (A-4) was used except that a dropping solution (a-4) in which 50 parts by weight of xylene, 100 parts by weight of xylene, and 9 parts by weight of tert-butylperoxy-2-ethylhexanoate were mixed was used. A polymer was obtained in the same manner as in Production Example -1). After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or lower, and 78 parts by weight of 1,1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz BEI), methoquinone 0.05 as a polymerization inhibitor An additional part by weight was added and reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (A-4). This copolymer had a weight average molecular weight of 20,000. The iodine value of the solid content was 43.

(Production Example 5 of leveling agent)
Instead of the dropping solution (a-1) in the production of the copolymer (A-1) in Production Example 1, 100 parts by weight of isobutyl acrylate, 160 parts by weight of normal butyl acrylate, 2-isocyanatoethyl A copolymer (a-5) was used except that 40 parts by weight of methacrylate, 100 parts by weight of xylene, and 9 parts by weight of tert-butylperoxy-2-ethylhexanoate were mixed. A polymer was obtained by the same method as in Production Example A-1). After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or less, 14 parts by weight of allyl alcohol and 0.05 part by weight of methoquinone as a polymerization inhibitor were added, and the mixture was reacted at 80 ° C. for 5 hours. Since the isocyanate equivalent was 0.03 mmol / g, it was confirmed that the reaction between the hydroxyl group of allyl alcohol and the isocyanate group in the polymer had ended. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (A-5). The weight average molecular weight of this copolymer was 18,000. The iodine value of the solid content was 19.

(Production Example 6 of leveling agent)
Charge 100 parts by weight of xylene and 0.1 parts by weight of boron trifluoride complex salt into a 1000 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen gas inlet, and introduce nitrogen gas. The temperature was raised to 30 ° C. Thereto was added dropwise a solution (a-6) in which 270 parts by weight of isobutyl vinyl ether and 30 parts by weight of 2- (2-vinyloxyethoxy) ethyl acrylate (trade name: VEEA) were mixed. Using a funnel, the solution was added dropwise at a constant speed in 3 hours while maintaining 30 ° C. After maintaining the same temperature for 30 minutes after completion of dropping, 0.2 parts by weight of 25% aqueous ammonia and 60 parts by weight of ion-exchanged water were added and stirred for 30 minutes. Stirring was stopped and the mixture was allowed to stand for 4 hours, and then the lower aqueous phase was separated. Further, 60 parts by weight of water was added for washing and separation, and then residual water and xylene were distilled off under reduced pressure. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (A-6). This copolymer had a weight average molecular weight of 4,000. The iodine value of the solid content was 13.
The production comparative examples of leveling agents are shown below.

(Production Comparative Example 1 of leveling agent)
In a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, 200 parts by weight of xylene was charged, and the temperature was raised to 120 ° C. while introducing nitrogen gas. Thereto, 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of 2-hydroxyethyl acrylate, 100 parts by weight of xylene, 30 parts by weight of tert-butylperoxy-2-ethylhexanoate The dropping solution (b-1) in which the parts were mixed was dropped at a constant rate over 2 hours with a dropping funnel. After completion of the dropwise addition, the mixture was reacted for 2 hours while maintaining at 120 ° C. to obtain a polymer. After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or lower, 20 parts by weight of 2-isocyanatoethyl acrylate, and 0.05 parts by weight of methoquinone as a polymerization inhibitor were added and reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (B-1). The weight average molecular weight of this copolymer was 1600. The iodine value of the solid content was 11.

(Production Comparative Example 2 of Leveling Agent)
In a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, 60 parts by weight of xylene was charged, and the temperature was raised to 95 ° C. while introducing nitrogen gas. There, 70 parts by weight of 2-ethylhexyl acrylate, 200 parts by weight of normal butyl acrylate, 30 parts by weight of 4-hydroxybutyl acrylate, 20 parts by weight of xylene, 2 of tert-butylperoxy-2-ethylhexanoate The dropping solution (b-2) mixed with parts by weight was added dropwise at a constant rate over 2 hours using a dropping funnel. After completion of the dropwise addition, the mixture was reacted for 1 hour while maintaining at 95 ° C., then heated to 115 ° C. and reacted for 4 hours to obtain a polymer. After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or less, 29 parts by weight of 2-isocyanatoethyl methacrylate and 0.05 part by weight of methoquinone as a polymerization inhibitor were added, and reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (B-2). The weight average molecular weight of this copolymer was 110,000. The iodine value of the solid content was 14.

(Production Comparative Example 3 of leveling agent)
Instead of the dropping solution (a-1) in the production of the copolymer (A-1) in Production Example 1, 70 parts by weight of ethyl acrylate, 100 parts by weight of isobutyl acrylate, and 2-hydroxyethyl acrylate A copolymer (A-) was used except that a dropping solution (b-3) in which 130 parts by weight, 100 parts by weight of xylene and 9 parts by weight of tert-butylperoxy-2-ethylhexanoate were mixed was used. A polymer was obtained by the same method as in Production Example 1). After completion of the polymerization reaction, the reaction mixture was cooled to 80 ° C. or lower, 295 parts by weight of 1,1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz BEI), and 0.1% of methoquinone as a polymerization inhibitor. An additional 05 parts by weight was reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (B-3). The weight average molecular weight of this copolymer was 30,000. The iodine value of the solid content was 105.

(Production Comparative Example 4 for Leveling Agent)
150 parts by weight of ethyl acrylate, 146 parts by weight of normal butyl acrylate, 2-hydroxyethyl acrylate in place of the dropping solution (a-1) in the production of copolymer (A-1) in Production Example 1 The copolymer (A-4) was used except that a dripping solution (b-4) in which 4 parts by weight of xylene, 100 parts by weight of xylene, and 9 parts by weight of tert-butylperoxy-2-ethylhexanoate were mixed was used. A polymer was obtained in the same manner as in Production Example -1). After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or lower, and 4 parts by weight of 2-isocyanatoethyl acrylate and 0.05 part by weight of methoquinone as a polymerization inhibitor were added and reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (B-4). The weight average molecular weight of this copolymer was 9,000. The iodine value of the solid content was 2.

  Compounding ingredients for the ultraviolet curable film forming composition shown in Table 1 and leveling agents of the copolymer liquids (A-1) to (A-6) and (B-1) to (B-4). An ultraviolet curable film-forming composition was prepared and used for a leveling test.

(Preparation of UV-curing film-forming composition)
0.5 parts by weight of leveling agents ((A-1) to (A-6) and (B-1) to (B-4)) are added to the mixture of components for the ultraviolet curable film-forming composition shown in Table 1. Were added and stirred for 2 minutes at 2,000 rpm with a lab disper to prepare UV-curable film-forming compositions of Examples 1 to 6 and Comparative Examples 1 to 4, respectively. In addition, the mixture of only the component for ultraviolet curable film formation composition was made into the comparative example 5.

  Using these, performance tests for evaluating smoothness, volatile oil resistance, and water resistance were conducted.

(Smoothness evaluation)
After leaving it to stand in a cool and dark place for 1 hour, it was applied to a glass plate with a 125 μm applicator and cured using a high-pressure mercury lamp (80 w / cm, height 10 cm) under the condition of an ultraviolet light cumulative light quantity of 480 mJ / cm ² . The coating surface of the coated plate was visually observed to evaluate smoothness. The smoothness evaluation was evaluated in five stages, with 5 being very excellent in smoothness, 4 being slightly excellent, 3 being excellent, 2 being slightly poor, and 1 being extremely poor.

(Volatile oil resistance evaluation)
The coating surface of the coated plate obtained in the same manner as in the smoothness evaluation was lightly wiped several times with gauze soaked with normal hexane. The whitening property of the wiped part was visually observed to evaluate the volatile oil resistance. The volatile oil resistance evaluation was evaluated in three stages, with ◯ indicating no whitening, Δ indicating slightly whitening, and X indicating marked whitening. In addition, if the film was already cloudy before wiping, it was determined that the evaluation was impossible.

(Water resistance evaluation)
The coated plate obtained in the same manner as in the smoothness evaluation was immersed in a hot water bath at 80 ° C. for 1 hour, then stopped heating, slowly cooled to room temperature, taken out from the water bath and dried at room temperature, and the water-immersed part was whitened. Was visually observed. The water resistance was evaluated in three stages, with ◯ indicating no whitening, Δ indicating slightly whitening, and X indicating marked whitening. In addition, it was determined that evaluation was not possible if the film was already cloudy before immersion.

  Table 2 shows the performance test results of the ultraviolet curable film-forming composition containing a leveling agent.

  As is apparent from Table 2, the film of the example in which the composition containing the leveling agent of the present invention was cured was smoother and more resistant to volatile oil than the film of the comparative example in which the composition to which the present invention was not applied was cured. The water resistance was excellent.

  An example in which an antifoaming agent was prototyped as a surface conditioner for an active energy ray curable film forming composition, an active energy ray curable film forming composition containing the same was prepared, and then cured to form a film. Indicates.

  First, the manufacture example of the antifoamer which is a surface conditioner of this invention is shown below.

(Production Example 7 of antifoaming agent)
In a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas blowing port, 80 parts by weight of xylene was charged, and the temperature was raised to 105 ° C. while introducing nitrogen gas. There, 170 parts by weight of lauryl methacrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of 2-hydroxyethyl acrylate, 60 parts by weight of xylene, 4 parts by weight of tert-butylperoxy-2-ethylhexanoate The dropping solution (c-1) in which the parts were mixed was dropped at a constant rate over 2 hours with a dropping funnel. After completion of the dropwise addition, the mixture was reacted for 1 hour while maintaining at 105 ° C., then heated to 115 ° C. and reacted for 4 hours to obtain a polymer. After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or lower, 20 parts by weight of 2-isocyanatoethyl acrylate and 0.05 part by weight of methoquinone as a polymerization inhibitor were added, and reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (C-1). The weight average molecular weight of this copolymer was 40,000. The iodine value of the solid content was 11.

(Production Example 8 of antifoaming agent)
Instead of the dropping solution (c-1) in the production example of the copolymer (C-1), 100 parts by weight of lauryl methacrylate, 170 parts by weight of stearyl methacrylate, 30 parts by weight of methacrylic acid, 60 parts by weight of xylene, Except for using a dropping solution (c-2) mixed with 4 parts by weight of tert-butylperoxy-2-ethylhexanoate, the same method as in the production example of copolymer (C-1) was used. A polymer was obtained. After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or less, and 62 parts by weight of 4-hydroxybutyl glycidyl ether acrylate, 1 part by weight of triethylamine as a catalyst, and 0.05 parts by weight of methoquinone as a polymerization inhibitor were added for 7 hours at 80 ° C. Reacted. The acid value was 4.3 mg · KOH / g, confirming the completion of the reaction. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene liquid (C-2). The weight average molecular weight of this copolymer was 41,000. The iodine value of the solid content was 21.

(Production Example 9 of antifoaming agent)
Instead of the dropping solution (c-1) in the production of the copolymer (C-1) in Production Example 8, 100 parts by weight of lauryl methacrylate, 170 parts by weight of 2-ethylhexyl acrylate, Plaxel FA5 (Daicel) 100 parts by weight of a hydroxyl group-containing acrylate in which 5 mol of caprolactone is added to 2-hydroxyethyl acrylate), 60 parts by weight of xylene, and 4 parts by weight of tert-butylperoxy-2-ethylhexanoate Except having used the mixed dripping solution (c-3), the polymer was obtained by the method similar to the manufacture example of a copolymer (C-1). After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or lower, 20 parts by weight of 2-isocyanatoethyl methacrylate and 0.05 part by weight of methoquinone as a polymerization inhibitor were added, and reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a xylene solution (C-3) of a copolymer. The copolymer had a weight average molecular weight of 38,000. The iodine value of the solid content was 10.

(Defoaming agent production example 10)
Instead of the dropping solution (c-1) in the production of the copolymer (C-1) in Production Example 8, 250 parts by weight of stearyl methacrylate, 50 parts by weight of 4-hydroxybutyl acrylate, 60 parts of xylene Similar to the production example of the copolymer (C-1), except that the dropping solution (c-4) in which 4 parts by weight of tert-butylperoxy-2-ethylhexanoate was mixed was used. A polymer was obtained by this method. After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or lower, 78 parts by weight of 1,1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz BEI), and 0. of methoquinone as a polymerization inhibitor. An additional 05 parts by weight was reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (C-4). The weight average molecular weight of this copolymer was 54,000. The iodine value of the solid content was 43.

(Production Example 11 of antifoaming agent)
Instead of the dropping solution (c-1) in the production of the copolymer (C-1) in Production Example 8, 160 parts by weight of 2-ethylhexyl acrylate, 100 parts by weight of normal butyl acrylate, 2-isocyanate Except for using a dropping solution (c-5) in which 40 parts by weight of natoethyl methacrylate, 60 parts by weight of xylene, and 4 parts by weight of tert-butylperoxy-2-ethylhexanoate were used, A polymer was obtained in the same manner as in the production example of coalesced (C-1). After completion of the polymerization reaction, the reaction mixture was cooled to 80 ° C. or lower, 14 parts by weight of allyl alcohol and 0.05 part by weight of methoquinone as a polymerization inhibitor were added and reacted at 80 ° C. for 5 hours. Since the NCO equivalent was 0.03 mmol / g, it was confirmed that the reaction between the hydroxyl group of allyl alcohol and the isocyanate group in the polymer was completed. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (C-5). The weight average molecular weight of this copolymer was 51,000. The iodine value of the solid content was 19.

(Production Example 12 of antifoaming agent)
A 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas blowing port was charged with 100 parts by weight of xylene and 0.04 parts by weight of boron trifluoride complex salt, and nitrogen gas was introduced. The temperature was raised to 30 ° C. A dripping solution in which 150 parts by weight of lauryl vinyl ether, 100 parts by weight of isobutyl vinyl ether, and 50 parts by weight of 2- (2-vinyloxyethoxy) ethyl methacrylate (manufactured by Nippon Shokubai, trade name: VEEM) were mixed ( c-6) was dripped at a constant rate in 3 hours while maintaining 30 ° C. with a dropping funnel. After maintaining the same temperature for 30 minutes after the completion of dropping, 0.2 parts by weight of 25% aqueous ammonia and 60 parts by weight of ion-exchanged water were added and stirred for 30 minutes. Stirring was stopped and the mixture was allowed to stand for 4 hours, and then the lower aqueous phase was separated. Further, 60 parts by weight of water was added for washing and separation, and then residual water and xylene were distilled off under reduced pressure. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (C-6). This copolymer had a weight average molecular weight of 12,000. The iodine value of the solid content was 13.

  The manufacture comparative example of the antifoamer was shown below.

(Production Comparative Example 5 for antifoaming agent)
In a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, 200 parts by weight of xylene was charged, and the temperature was raised to 120 ° C. while introducing nitrogen gas. There, 170 parts by weight of lauryl methacrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of 2-hydroxyethyl acrylate, 100 parts by weight of xylene, 30 parts by weight of tert-butylperoxy-2-ethylhexanoate The dropping solution (d-1) in which the parts were mixed was dropped at a constant rate over 2 hours with a dropping funnel. After completion of the dropwise addition, the mixture was reacted for 2 hours while maintaining at 120 ° C. to obtain a polymer. After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or lower, 20 parts by weight of 2-isocyanatoethyl acrylate and 0.05 part by weight of methoquinone as a polymerization inhibitor were added, and reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (D-1). The copolymer had a weight average molecular weight of 1800. The iodine value of the solid content was 10.

(Production Comparative Example 6 for antifoaming agent)
In a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, 60 parts by weight of xylene was charged, and the temperature was raised to 95 ° C. while introducing nitrogen gas. There, 70 parts by weight of stearyl methacrylate, 200 parts by weight of normal butyl acrylate, 30 parts by weight of 4-hydroxybutyl acrylate, 20 parts by weight of xylene, 2 parts by weight of tert-butylperoxy-2-ethylhexanoate Was added dropwise at a constant rate over 2 hours using a dropping funnel. After completion of the dropwise addition, the mixture was reacted for 1 hour while maintaining at 95 ° C., then heated to 115 ° C. and reacted for 4 hours to obtain a polymer. After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or less, 29 parts by weight of 2-isocyanatoethyl methacrylate and 0.05 part by weight of methoquinone as a polymerization inhibitor were added, and reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene liquid (D-2). The weight average molecular weight of this copolymer was 105,000. The iodine value of the solid content was 14.

(Production Comparative Example 7 for antifoaming agent)
Instead of the dropping solution (c-1) in the production of the copolymer (C-1) in Production Example 8, 130 parts by weight of lauryl methacrylate, 40 parts by weight of stearyl methacrylate, and 2-hydroxyethyl acrylate A copolymer (C--) was used except that a dripping solution (d-3) in which 130 parts by weight, 60 parts by weight of xylene and 4 parts by weight of tert-butylperoxy-2-ethylhexanoate were mixed was used. A polymer was obtained by the same method as in Production Example 1). After completion of the polymerization reaction, the reaction mixture was cooled to 80 ° C. or lower, 295 parts by weight of 1,1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz BEI), and 0.1% of methoquinone as a polymerization inhibitor. An additional 05 parts by weight was reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (D-3). The weight average molecular weight of this copolymer was 40,000. The iodine value of the solid content was 105.

(Production Comparative Example 8 for antifoaming agent)
Instead of the dropping solution (c-1) in the production of the copolymer (C-1) in Production Example 8, 146 parts by weight of stearyl methacrylate, 150 parts by weight of normal butyl acrylate, 2-hydroxyethyl acrylate The copolymer (C-4) was used except that a dripping solution (d-4) in which 4 parts by weight of xylene, 60 parts by weight of xylene and 4 parts by weight of tert-butylperoxy-2-ethylhexanoate were mixed was used. A polymer was obtained in the same manner as in Production Example -1). After completion of the polymerization reaction, the mixture was cooled to 80 ° C. or lower, and 4 parts by weight of 2-isocyanatoethyl acrylate and 0.05 part by weight of methoquinone as a polymerization inhibitor were added and reacted at 80 ° C. for 5 hours. It was confirmed that the peak 2270 cm ⁻¹ of the isocyanate group by IR disappeared. The solid content was adjusted to 30% by diluting with xylene to produce a copolymer xylene solution (D-4). The weight average molecular weight of this copolymer was 49,000. The iodine value of the solid content was 2.

  Compounding ingredients for the ultraviolet curable film-forming composition shown in Table 3, and antifoaming agents of the copolymer liquids (C-1) to (C-6) and (D-1) to (D-4) Was used to prepare an ultraviolet curable film-forming composition, and an antifoaming test was conducted.

(Preparation of UV-curing film-forming composition)
0.5 weight of defoamers ((C-1) to (C-6) and (D-1) to (D-4)) are added to the mixture of components for ultraviolet curable film-forming composition shown in Table 3. Partly added and stirred at 2,000 rpm for 2 minutes with a lab disper to prepare UV curable film-forming compositions of Examples 7-12 and Comparative Examples 6-9, respectively. In addition, the mixture of only the component for ultraviolet curable film formation composition was made into the comparative example 10.

  Using these, performance tests for evaluating defoaming properties, volatile oil resistance, and water resistance were conducted.

(Defoaming evaluation)
After stirring, the UV-cured film-forming composition added with the antifoaming agent was immediately poured into a 25 mL specific gravity cup, and the weight immediately after stirring of the antifoaming agent-added composition that satisfied this was measured. On the other hand, an ultraviolet-curing film-forming composition without addition of an antifoaming agent is allowed to stand for several hours after stirring, and then the composition containing no foam is poured into a specific gravity cup to satisfy the composition. The weight of the object after standing was measured. When the weight of the composition with no defoamer added was set to 100%, the ratio of the weight immediately after stirring of the composition with the defoamer added was calculated. The defoaming property evaluation was evaluated in three stages, where the ratio is 97% or more, ◯, less than 97% is 95% or more, and less than 95% is ×.

  Volatile oil resistance and water resistance test methods and evaluation criteria were the same as the performance test of the leveling agent.

  Table 4 shows the performance test results of the ultraviolet curable film-forming composition containing an antifoaming agent.

  As is apparent from Table 4, the film of the example in which the composition containing the antifoaming agent of the present invention was cured was more antifoaming and resistant than the film of the comparative example in which the composition other than the present invention was cured. It was excellent in volatile oil resistance and water resistance.

  The surface conditioner for an active energy ray-curable film-forming composition of the present invention is used to form films on various substrates such as various plastic members, wood, building materials such as metal and concrete, and bodies of automobiles. Added to the resulting composition.

Claims (7)

And the main chain with the addition copolymerization, surface conditioning antifoaming agent comprising a (meth) non-volatile components copolymer is containing chromatic having a side chain having at least one kind of unsaturated groups acryloyl groups and alkenyl groups 0.02% of the non-volatile component relative to the film-forming component when the non-volatile component in the surface conditioning agent is 30% as a solid content while containing an agent and a solvent-free active energy ray-cured film-forming component. An active energy ray-cured film-forming composition that is cured with active energy rays in the absence of a solvent,
The copolymer is, while the weight average molecular weight of that and 2,000-100,000, is intended to the iodine value and 3-100,
The copolymer forms the main chain by the addition copolymerization of a (meth) acrylic acid derivative having a reactive functional group and an unsaturated aliphatic group-containing derivative not having a reactive functional group. A copolymer that forms the side chain by reaction of a compound having a binding functional group that reacts with and binds to the reactive functional group that the unsaturated functional group has, and the reactive functional group. (Meth) acrylic acid derivatives having a group are converted into 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-methacryloyloxyethyl-2-hydroxyl Pyrphthalate, caprolactone added to 2-hydroxyethyl (meth) acrylate (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, isocyanatoalkyl ( Compound in which isocyanate group of meth) acrylate is blocked with methyl ethyl ketoxime, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl glycidyl ether acrylate, (meth) acrylic acid, 2- (Meth) acryloyloxyethyl succinic acid or 2-methacryloyloxyethyl hexahydrophthalic acid, and the unsaturated aliphatic group-containing derivative having no reactive functional group is methyl (meth) acrylate Ethyl (meth) acrylate, normal propyl (meth) acrylate, isopropyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, normal octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) ) Acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methoxy Ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-octoxyethyl (meta Acrylate, 2-lauroxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, (meth) acrylic acid methoxypolyethylene glycol ester, ( (Meth) acrylic acid methoxypolypropylene glycol ester, (meth) acrylic acid methoxypoly (ethylene-propylene) glycol ester, (meth) acrylic acid methoxypoly (ethylene-tetramethylene) glycol ester, (meth) acrylic acid butoxypoly (ethylene-propylene) glycol Ester, (Meth) acrylic acid octoxypoly (ethylene-propylene) glycol ester, (Meth) acrylic acid lauroxypolyethylene glycol ester, (Meth) Lauroxy poly (ethylene-propylene) glycol acrylate, acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, acroylmorpholine, styrene, α-methylstyrene, chlorostyrene , Vinyl toluene, vinyl acetate, vinyl propionate, methyl vinyl ether, ethyl vinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, tertiary butyl vinyl ether, normal octyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether , Stearyl vinyl ether, salt A compound having vinyl, vinylidene chloride, chloroprene, propylene, butadiene, or isoprene and having the binding functional group and the unsaturated group is represented by 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone (Meth) acrylate added to 2-hydroxyethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, glycidyl (Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl glycidyl ether acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, or 2-methacryloyloxy Ethyl hexahydrophthalic acid,
Or
The copolymer forms the main chain by the addition copolymerization of unsaturated aliphatic groups of an unsaturated aliphatic group-containing derivative having a (meth) acryloyl group and another unsaturated aliphatic group-containing derivative. The unsaturated aliphatic group-containing derivative having a (meth) acryloyl group is 2- (2-vinyloxyethoxy) ethyl acrylate or 2- (2-vinyloxyethoxy) ethyl methacrylate. The other unsaturated aliphatic group-containing derivative is styrene, α-methylstyrene, chlorostyrene, vinyl toluene, vinyl acetate, vinyl propionate, methyl vinyl ether, ethyl vinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, Isobutyl vinyl ether, tertiary butyl vinyl Active energy ray characterized by being ether, normal octyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, or diallyl phthalate Cured film forming composition . The copolymer is, actinic radiation-curable film-forming composition according to claim 1, wherein the random copolymer Karadadea Rukoto. The copolymer is that having a said reactive functional group and (meth) acrylic acid derivative, by the addition copolymerization said unsaturated aliphatic group-containing derivatives not having reactive functional groups, the after forming the main chain, by reacting a compound having said unsaturated group to the binding functional group, the binding functional group to the reactive functional group is attached to the reaction, whereby the The active energy ray-curable film-forming composition according to claim 1 , wherein the composition is formed by a step of forming a side chain . The copolymer is, the (meth) and the unsaturated aliphatic group-containing derivative having an acryloyl group, and said another unsaturated aliphatic group-containing derivative, by the addition copolymerization, their unsaturated aliphatic The active energy ray-curable film forming composition according to claim 1 , wherein the composition is formed by a step of forming the main chain by reacting groups . The active energy ray-curable film forming composition according to any one of claims 1 to 4, wherein the copolymer has an iodine value of 6 to 50 . Resin in which the active energy ray cured film forming component is a resin forming component that is epoxy acrylate, a resin forming component that is urethane acrylate, a resin forming component that is polyester acrylate, and a blend of urethane acrylate and trimethylolpropane triacrylate active energy ray curable film-forming composition according to any one of claims 1 to 5, either der wherein Rukoto selected from formed components. A film obtained by applying the active energy ray-curable film-forming composition according to claim 1 on a substrate is cured by irradiation with an active energy ray selected from ultraviolet rays, infrared rays, far infrared rays, electron beams, and radiations. Characterized cured film.