JP2018024764A - Impact absorbing agent for coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an impact absorbing agent which does not cause such a failure that a coated film hardness is lowered by blended with a coating material, imparts impact resistance to the coated film, and does not exert an adverse effect on appearance of the coated film; a coating composition containing the impact absorbing agent; and a coated film formation method by the coating composition.SOLUTION: A copolymer is effective as an impact absorbing agent which is obtained by polymerization of 100 pts.mass of a monomer mixture formed of 10-100 pts.mass of at least one macromonomer (A) selected from diacrylate having a glass transition temperature Tg of 0°C or lower and -80°C or higher and a dimethacrylate macromonomer and 0-90 pts.mass of at least one monomer (B) which has a glass transition temperature Tg of 40°C or higher and 250°C or lower when formed into a homopolymer, and is selected from acrylate having C1-C18 straight chain, branched or cyclic hydrocarbon group, methacrylate and styrenes. The copolymer is added to a coating composition to improve impact resistance of a coated film.SELECTED DRAWING: None

Description

  The present invention relates to a shock absorber for paints which, when added to a paint, imparts shock absorption to the paint film without reducing the appearance and hardness of the paint film.

  For the purpose of protecting the substrate, a technique of forming a paint film on the substrate surface is widely used. However, when solid objects such as metal, stone, concrete collide with the paint film, the paint film may be broken and peeled off. If water enters the peeled part, the base material will rust or corrode. Deterioration progresses. For example, metal objects such as automobile bodies, guardrails, and road signs are subject to so-called chipping, which is a so-called chipping, in which a coating film is cracked or peeled off due to stone splashing from the road surface. Especially in the cold season, rock salt and gravel are often laid on the road in order to prevent freezing and slipping, and the problem is that these solid particles rolled up when the vehicle travels collide with the coating film and chip.

  As a means for preventing these chipping phenomena, a technique of blending a paint with a polymer having a low glass transition temperature (hereinafter abbreviated as Tg) for the purpose of absorbing the impact on the coating film (Patent Documents 1 and 2), A technique using a styrene-butadiene copolymer (Patent Documents 3, 4 and 5) and a urethane dispersion (Patent Documents 6 and 7) has been used.

JP-A 62-169869 JP-A-1-197569 JP 59-75954 A JP-A-2-28269 JP-A-4-202262 JP-A-2005-48116 JP 2006-136792 A

  However, the conventional method cannot sufficiently overcome the chipping particularly in the cold season. In addition, there is a problem that the hardness and strength of the coating film are reduced by blending a soft material into the paint.

  Accordingly, an object of the present invention is to impart impact absorption at low temperatures to a coating film without reducing coating film hardness.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have added a chemically crosslinked polymer having a three-dimensional network structure obtained by polymerizing a bifunctional macromonomer having a low Tg to the impact absorbing ability. Found a dramatic improvement. Further, it has been found that even when this cross-linked polymer is added to a coating material, impact resistance is imparted to the coating film and no adverse effect is exerted on the coating film appearance without causing a problem that the coating film hardness decreases.

That is, the first invention of the present invention is
10 to 100% by mass of at least one macromonomer (A) selected from diacrylate and dimethacrylate macromonomers having a Tg of 0 ° C. or lower and −80 ° C. or higher, and a Tg of 40% when a homopolymer is used. 0 to 90% by mass of at least one monomer (B) selected from acrylates, methacrylates, and styrenes having a linear, branched or cyclic hydrocarbon group having a carbon number of C1 to C18 and not lower than 250 ° C. And a monomer blended copolymer, which is added to the coating composition to improve the impact resistance of the coating film.

  The second invention contains the macromonomer component (A), the monomer component (B), and the monomer component (C) having a polymerizable unsaturated bond copolymerizable therewith, and the macromonomer (A). And a copolymer obtained by polymerizing a mixture in which the monomer (C) is 50 parts by mass or less with respect to 100 parts by mass in total of the monomer (B), which is added to the coating composition and added to the coating composition. It is a shock absorber that improves impact properties.

  A third invention is characterized in that the number average molecular weight of the diacrylate and dimethacrylate macromonomer (A) is 400 to 15000, and is added to a coating composition to improve the impact resistance of the coating film. It is a shock absorber.

  4th invention is a coating composition which contains said shock absorber 1-20 mass% with respect to the resin solid content contained in a coating material.

  A fifth invention is a coating film characterized in that the coating composition is formed by being applied to a substrate and cured.

  A sixth invention is a method for forming a multilayer coating film, wherein a top coating is applied to the entire surface or a part of the coating film.

  7th invention is the multilayer coating film obtained by said method.

  By adding the impact absorber for paints of the present invention to the paint, it is possible to impart impact resistance to the paint film without adverse effects such as a decrease in coating film hardness and a decrease in coating film appearance. .

  Each component constituting the copolymer of the present invention will be described.

Macromonomer (A) “Diacrylate and Dimethacrylate Macromonomer”
Examples of the diacrylate and dimethacrylate macromonomer (A) having a Tg of 0 ° C. or lower and −80 ° C. or higher include SR644 (polypropylene glycol dimethacrylate, number average molecular weight (hereinafter abbreviated as Mn) 660 manufactured by Sartomer, Tg : -5 ° C), Shin-Nakamura Chemical Co., Ltd. APG-400 (polypropylene glycol diacrylate, Mn620, Tg: -8 ° C), APG-700 (polypropylene glycol diacrylate, Mn1020, Tg: -32 ° C), Hitachi Chemical FA-023M (Ethoxylate Polypropylene Glycol Dimethacrylate, Mn 1400, Tg: -47 ° C), Bremer PDP-400N (Polypropylene Glycol Dimethacrylate, Mn 610, Tg: -11 ° C), Bremer PDT-6 Polyalkylene glycol di (meth) acrylates such as 0 (polytetramethylene glycol dimethacrylate, Mn1000, Tg: −53 ° C.); BAC-45 (polybutadiene diacrylate, Mn4750, Tg: −, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 34 ° C), TEAI-1000 manufactured by Nippon Soda Co., Ltd. (both end acrylic group-introduced polybutadiene urethane bond type, Mn2880, Tg: -14 ° C), TE-2000 (both end methacryl group-introduced polybutadiene urethane bond type, Mn3900, Tg: 9 ° C)
Polybutadiene di (meth) acrylates such as CN307 (polybutadiene diacrylate, Mn4190, Tg: -34 ° C) manufactured by Sartomer; CN9004 (aliphatic urethane diacrylate, Mn11000, Tg: -76 ° C), CN9014 (hydrophobic fat) Group urethane diacrylate, Mn9400, Tg: -41 ° C) and the like. These macromonomers can be used alone or in combination of two or more.

  400-15000 are preferable and, as for Mn of a macromonomer (A), 500-11000 are more preferable. By making Mn of (A) 400 or more, impact absorbability can be imparted satisfactorily. Moreover, it is preferable that Mn of (A) is 15000 or less at the point of the hardness of an additional coating film. By setting the Mn of (A) to 400 to 15000, it is possible to obtain an impact absorber for paint that has both impact absorbability and coating strength.

  10-100 mass% is preferable, as for content of a macromonomer (A), 10-95 is more preferable, More preferably, it is 20-90 mass%. When it is less than 10% by mass, good impact resistance is not recognized.

Monomer (B) "acrylates, methacrylates and styrenes"
Monomer (B) selected from acrylates, methacrylates, and styrenes having a Tg of 40 ° C. or more and 250 ° C. or less, and having a C1-C18 linear, branched or cyclic hydrocarbon group, as a homopolymer As, for example, adamantyl methacrylate (Tg: 250 ° C.), dicyclopentenyl methacrylate (Tg: 175 ° C.), dicyclopentanyl methacrylate (Tg: 175 ° C.), adamantyl acrylate (Tg: 153 ° C.), isobornyl methacrylate ( Tg: 150 ° C., dicyclopentenyl acrylate (Tg: 120 ° C.), dicyclopentanyl acrylate (Tg: 120 ° C.), phenyl methacrylate (Tg: 110 ° C.), methyl methacrylate (Tg: 105 ° C.), isobornyl Acrylate (Tg: 97 ° C.), Chlohexyl methacrylate (Tg: 83 ° C), isopropyl methacrylate (Tg: 83 ° C), ethyl methacrylate (Tg: 65 ° C), benzyl methacrylate (Tg: 54 ° C), isobutyl methacrylate (Tg: 48 ° C), tertiary butyl acrylate (Meth) acrylates such as (Tg: 41 ° C.); styrene derivatives such as styrene (Tg: 100 ° C.), 2-methylstyrene (Tg: 136 ° C.), tertiary butyl butylstyrene (Tg: 149 ° C.), etc. Is mentioned. These monomers can be used alone or in combination of two or more.

  0-90 mass% is preferable, as for content of a monomer (B), 5-90 is more preferable, More preferably, it is 10-80 mass%. When it is more than 90% by mass, impact resistance is not recognized.

Monomer (C) "Other polymerizable unsaturated monomer"
The copolymer of the present invention may contain the polymerizable unsaturated monomer (C) in a range of 50 parts by mass or less with respect to 100 parts by mass in total of the macromonomer (A) and the monomer (B). By copolymerizing the polymerizable unsaturated monomer (C), the dispersibility and stability in the coating composition can be improved, and the reactivity with the coating resin component can be imparted. Examples of the polymerizable unsaturated monomer (C) include, for example, carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and β-carboxyethyl acrylate; 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1-hydroxy-1-methylmethyl (meth) acrylate, 2-hydroxy-1-methylethyl (meth) Hydroxyl-containing (meth) acrylates such as acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, 1-hydroxy-2-propyl (meth) acrylate, and 2 (2-hydroxyethoxy) ethyl (meth) acrylate Class: Acrylamide, N-methyl acrylate Luamide, N-methylmethacrylamide, N-methylolacrylamide butyl ether, N-methylolmethacrylamide butyl ether, N-ethylacrylamide, N-ethylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-isopropyl Acrylamide, N-isopropylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylamide, diacetoneacrylamide, diacetonemethacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N -Hydroxyethyl methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-di Ethylacrylamide, N, N-diethylmethacrylamide, N-methyl, N-ethylacrylamide, N-methyl, N-ethylmethacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide, N -Methylol acrylamide methyl ether, N-methylol methacrylamide methyl ether, N-methylol acrylamide ethyl ether, N-methylol methacrylamide ethyl ether, N-methylol acrylamide propyl ether, N-methylol methacrylamide propyl ether, acryloyl morpholine, methacryloyl morpholine, etc. (Meth) acrylamides; methyl acrylate, ethyl acrylate, normal propyl (meth) acrylate, isop Pyracrylate, normal butyl (meth) acrylate, isobutyl acrylate, hexyl (meth) acrylate, normal octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) Hydrocarbon group-containing (meth) acrylates such as acrylate, stearyl (meth) acrylate, cyclohexyl acrylate, benzyl acrylate and the like; phenoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- Ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-octoxyethyl (meth) acrylate, 2-lauroxyethyl (meth) acrylate, 3- Toxibutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypoly (ethylene-propylene) glycol (meth) acrylate, Contains ether groups such as methoxypoly (ethylene-tetramethylene) glycol (meth) acrylate, butoxypoly (ethylene-propylene) glycol (meth) acrylate, octoxypoly (ethylene-propylene) glycol (meth) acrylate, lauroxypolyethyleneglycol (meth) acrylate Mono (meth) acrylates; ethyl vinyl ether, normal propyl vinyl ether, Vinyl ethers such as sopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, tertiary butyl vinyl ether, normal octyl vinyl ether, 2-ethylhexyl vinyl ether, 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether; vinyl acetate, vinyl propionate, caproic acid Vinyl esters and allyl compounds such as vinyl, vinyl octylate, diallyl phthalate; dimethyl maleate, diethyl maleate, diisopropyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, monomethyl maleate, monobutyl maleate, Maleic acid alkyl esters such as mono-2-ethylhexyl maleate; Alkyl esters of fumaric acid such as chill, diethyl fumarate, diisopropyl fumarate, diisobutyl fumarate, di-2-ethylhexyl fumarate, monoethyl fumarate, monobutyl fumarate; dibutyl itaconate, di-2-ethylhexyl itaconate, itacon Itaconic acid alkyl esters such as monomethyl acid, monobutyl itaconate; reactive silicones having a methacryloyloxy group (Silaplane FM-0711, FM-0721 and FM-0725 manufactured by JNC Corporation; Toagosei Co., Ltd.) AK-5 and AK-30, manufactured by Shin-Etsu Silicone Co., Ltd .; X22-164A, X22-164B, and X22-164C); divinylbenzene, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) a Relate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Polyfunctional unsaturated monomers other than macromonomer (A) such as pentyl glycol di (meth) acrylate; (meth) acrylates containing glycidyl groups such as glycidyl (meth) acrylate and acrylic glycidyl ether; Reactive surfactant having a saturated group (Antox MS-60 manufactured by Nippon Emulsifier; Aqualon KH-10, KH-05 manufactured by Daiichi Kogyo Seiyaku, Ltd. Latemul PD-104 manufactured by Kao Corporation; manufactured by Sanyo Chemical Industries, Ltd. Elemiol RS-3000) Etc.

  As content of a polymerizable unsaturated monomer (C), it is preferable that it is 50 mass parts or less with respect to a total of 100 mass parts of a macromonomer (A) and a monomer (B). When it is more than 50 parts by mass with respect to 100 parts by mass of the total of the macromonomer (A) and the monomer (B), the effects of obtaining good impact resistance, coating film hardness and finished appearance are not recognized.

  In the present invention, “(meth) acrylate” means at least one selected from “acrylate” and “methacrylate”.

  As a method for synthesizing the copolymer used in the present invention, there are a solution polymerization method, a dispersion polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization method, and the like. An azo polymerization initiator or a peroxide is used. Since the present invention relates to the function of the copolymer, it is not limited by the synthesis method.

  In this specification, the number average molecular weight (Mn) and the weight average molecular weight (hereinafter abbreviated as Mw) are values calculated based on the molecular weight of standard polystyrene from the chromatogram measured by gel permeation chromatograph (GPC). is there. As the gel permeation chromatograph, “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) was used. As the columns, four columns of “TSKgel GMHxL” × 2, “TSKgel G-2500HxL”, “TSKgel G-2000HxL” (both manufactured by Tosoh Corporation), mobile phase: tetrahydrofuran, measurement temperature 40 ° C., flow rate: 1 cc / min, detector; RI.

  The copolymer of the present invention can have good impact absorbability when Mw is 50000 or more. When Mw is less than 50000, the impact absorbability decreases. However, a copolymer containing a large amount of a bifunctional macromonomer has a very high molecular weight, and molecular weight measurement by gel permeation chromatography (GPC) may not be possible.

The solubility parameter (hereinafter abbreviated as SP value) of the copolymer of the present invention is usually 8.0 to 12.0 (cal / cm ³ ) ^1/2 , preferably 9.0 to 11.0. .
The SP value of the copolymer is a value calculated by the method described in the Fedors method (Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154). As for the SP value of the copolymer, the SP value of each monomer constituting the copolymer is calculated by the above method, and the SP value of each monomer is calculated based on the volume fraction of the constituent monomer units. The average value. The SP value of the copolymer can be adjusted by appropriately adjusting the SP value and volume fraction of the monomer used.

  The impact absorber of the present invention may contain a surfactant as necessary in order to facilitate the dispersion of the copolymer into the coating material. Although it does not specifically limit as surfactant used, Nonionic surfactant and / or anionic surfactant etc. are mentioned.

  Examples of the nonionic activator include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ester, sorbitan aliphatic ester, polyoxyethylene sorbitan aliphatic ester, polyoxyethylene oxypropylene copolymer Etc. These may be used alone or in combination.

  Examples of the anionic activator include alkyl fatty acid salts, alkyl sulfate esters, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, sulfosuccinates, phosphate ester salts and the like. These may be used alone or in combination.

  The impact absorber of the present invention can contain a solvent as required in order to facilitate the dispersion of the copolymer into the paint. For example, hydrocarbon solvents such as xylene, toluene, solvent naphtha and cyclohexane; ketone solvents such as cyclohexanone and methyl isobutyl ketone; 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Ether solvents such as monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether; n-butyl acetate, isobutyl acetate, n-amyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3 Ester solvents such as methoxybutyl acetate; n-butyl alcohol Le, sec- butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, 3-methyl-3-alcohol solvent and water can be mentioned, such as methoxy butanol. These solvents may be used alone or in combination.

  The shock absorber of the present invention is not limited to the characteristics and purpose of the present invention, but other substances such as film-forming aids, dryers, antifouling agents, thickeners, antioxidants, ultraviolet absorbers, water resistance Other additives such as additives, antiseptic / antifungal agents, antifoaming agents, leveling agents, dispersants, flame retardants, adhesion improvers, colorants, antistatic agents, release agents, coupling agents, deodorants, fragrances and dyes An agent can be contained.

  The timing of adding the shock absorber according to the present invention to the paint is arbitrary, and can be added in the process of kneading the pigment or after the paint is produced.

  The addition amount of the shock absorber according to the present invention varies depending on the type of resin of the paint, the blending composition of the pigment, and the like. %, Preferably 5 to 15% by weight.

  If the amount added is less than 1% by mass, impact absorbability cannot be imparted. Further, if it is added in an amount of more than 20% by mass, it is not preferable because it adversely affects the hardness and appearance of the coating film or excessively thickens the paint.

  The coating composition to which the shock absorber according to the present invention is added may be in any form such as a solvent-based coating, a water-based coating, a solventless coating, and a powder coating.

Although the coating component mix | blended with this coating composition is not specifically limited, For example, resin, a hardening | curing agent, a pigment and dye, a dilution solvent, surfactant, a modifier, etc. are mentioned. If necessary, curing catalyst, sensitizer, antifoaming agent, viscosity modifier, dispersant, leveling agent, flame retardant, adhesion improver, colorant, antistatic agent, antioxidant, light stabilizer, Various additives such as a release agent and a coupling agent can be contained.

  Representative examples of resins include, for example, acrylic resins, polyester resins, urethane resins, alkyd resins, epoxy resins, amino resins, nitrocellulose resins, cellulose acetate butyrate resins, vinyl chloride / acetic acid. Such as vinyl copolymer resins, ketone resins or petroleum resins. These resins may be used only as a resin component, or may be used as a form dissolved or dispersed in an organic solvent or water.

  Resins are in the presence or absence of a catalyst, such as heat curable, ultraviolet curable, electron beam curable, oxidative curable, photocationic curable, peroxide curable, and acid / epoxy curable. It may be one that cures with a chemical reaction underneath, or may be one that forms a film only by volatilization of the diluting solvent.

  As a hardening | curing agent, an isocyanate compound, a melamine resin, an acid, a base, a polymerization initiator, water etc. are mentioned, for example.

  Examples of pigments and dyes include titanium dioxide, carbon black, chrome lead, cadmium yellow, ocher, titanium yellow, zinc chromate, dial, aluminosilicate, quinacridone, phthalocyanine, antroquinone, diketopyrrolopyrrole , Colored pigments composed of benzimidazolone and isoindolinone, metallic pigments (aluminum flakes, copper flakes, mica-like iron oxide, mica, scaly powder coated with metal oxide on mica, etc.) and calcium carbonate And extender pigments composed of barium sulfate, silicon dioxide, aluminum hydroxide, talc, organic fibers, glass powder and the like.

  Examples of the diluent solvent include hydrocarbon solvents such as xylene, toluene, and cyclohexane; ketone solvents such as cyclohexanone and methyl isobutyl ketone; 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether Ether solvents such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether; n-butyl acetate, isobutyl acetate, n-amyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Ester solvents such as 3-methoxybutyl acetate; n-butyl alcohol Le, sec- butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, 3-methyl-3-alcohol solvent and water can be mentioned, such as methoxy butanol. These solvents may be used alone or in combination.

  Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants, and reactive surfactants thereof. These surfactants may be used alone or in combination.

  Examples of the modifier include polyolefin, polystyrene, polyvinyl chloride, polyamide, polyimide, polyurethane, urea resin, polylactic acid, polyvinyl alcohol, polyvinyl acetate, acrylic resin, polysulfone, polycarbonate, ABS resin, AS resin, and silicone resin. Etc. These may be used alone or in combination.

  The coating film of the present invention is a film formed by drying or curing a coating film obtained by coating the coating composition of the present invention on a substrate.

  Although a base material is not specifically limited, A metal, wood, a plastics, rubber | gum, paper, glass, a stone material, a cement material, a mortar material, ceramics etc. are mentioned.

  The method for applying the coating composition is not particularly limited. For example, spray coating, spin coating, slit coating, dip coating, bar coating, doctor blade, roll coating, flow coating, die coating, electrodeposition coating, electrostatic coating (air atomization, rotary atomization), brush or roller coating, etc. Is mentioned.

  The coating film layer formed by the coating composition may be a single layer, or a number of coating films may be laminated. When forming a multilayer coating film, it may be applied after each coating layer has been cured, or may be cured simultaneously after being applied in a wet-on-wet system in which it is applied in an uncured state.

  The use of the coating composition containing the shock absorber of the present invention is not particularly limited, but can exhibit excellent shock absorption and coating film hardness, for example, automobiles, railway vehicles, ships, aircraft, It is suitably used for electrical equipment, building structures, construction equipment, automobile parts, home appliances, machines and the like.

  Hereinafter, the present invention will be specifically described with reference to examples. In addition, this invention is not restrict | limited at all by these Examples. Further, “%” and “part” in the examples represent “% by mass” and “part by mass” unless otherwise specified.

Example 1
In a 500 ml reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 110 parts of deionized water and Newcol 707-SFC (trade name, polyoxyethylene polycyclic phenyl ether sulfate as emulsifier) 2 parts of ester salt (manufactured by Nippon Emulsifier Co., Ltd.) were charged. Thereafter, the internal temperature was raised to 83 ° C. while stirring under a nitrogen gas stream. To the above dropping funnel, 90 parts of Blemmer PDP-400N (trade name, polypropylene glycol dimethacrylate: NOF Corporation) as a dripping solution (a-1), 10 parts of isobornyl methacrylate, Newcol 707-SFC (trade name) as an emulsifier , Polyoxyethylene polycyclic phenyl ether sulfate: manufactured by Nippon Emulsifier Co., Ltd.) and an emulsion comprising 100 parts of deionized water were charged. Next, the emulsion was uniformly added dropwise over 2 hours while maintaining the internal temperature of the reaction vessel at 83 ° C. At the same time, 50.5 parts of a 1% ammonium persulfate aqueous solution was uniformly added dropwise over 2 hours. After completion of dropping, the reaction was terminated after aging at 83 ° C. for 2 hours. After the reaction product was cooled, it was filtered through a 400 mesh stainless steel wire mesh, and the solid content was adjusted to 20% with deionized water to obtain an impact absorber [1].

Example 2
Instead of the dropping solution (a-1) of Example 1, 50 parts of APG-700 (trade name, polypropylene glycol diacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.) as the dropping solution (a-2), 50 parts of dicyclopentanyl methacrylate Example 1 except that an emulsified product comprising 13 parts of New Coal 707-SFC (trade name, polyoxyethylene polycyclic phenyl ether sulfate: Nippon Emulsifier Co., Ltd.) and 100 parts of deionized water was used as an emulsifier. A shock absorber [2] was obtained by the same method.

Example 3
Instead of the dropping solution (a-1) of Example 1, 50 parts of APG-700 (trade name, polypropylene glycol diacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.) as the dropping solution (a-3), 50 parts of isobornyl acrylate, The same as in Example 1 except that an emulsified product consisting of 13 parts of New Coal 707-SFC (trade name, polyoxyethylene polycyclic phenyl ether sulfate: Nippon Emulsifier Co., Ltd.) and 100 parts of deionized water was used as the emulsifier. The shock absorber [3] was obtained by the method described above.

Example 4
Instead of the dropping solution (a-1) of Example 1, 34 parts of Bremer PDP-400N (trade name, polypropylene glycol dimethacrylate: manufactured by NOF Corporation) as the dropping solution (a-4), FA-023M (trade name, Ethoxylate polypropylene glycol dimethacrylate (made by Hitachi Chemical Co., Ltd.) 33 parts, isobornyl methacrylate 33 parts, Newcol 707-SFC as an emulsifier (trade name, polyoxyethylene polycyclic phenyl ether sulfate: produced by Nippon Emulsifier Co., Ltd.) 12 A shock absorber [4] was obtained in the same manner as in Example 1 except that an emulsion comprising 100 parts of deionized water and 100 parts of deionized water was used.

Example 5
Instead of the dropping solution (a-1) of Example 1, 22 parts of FA-023M (trade name, ethoxylate polypropylene glycol dimethacrylate: manufactured by Hitachi Chemical Co., Ltd.) as a dropping solution (a-5), 68 parts of cyclohexyl methacrylate, methacrylic Implemented except using 10 parts of acid, 10 parts of Newcol 707-SFC (trade name, polyoxyethylene polycyclic phenyl ether sulfate: manufactured by Nippon Emulsifier Co., Ltd.) as an emulsifier and 100 parts of deionized water. A shock absorber [5] was obtained in the same manner as in Example 1.

Example 6
Instead of dropping solution (a-1) of Example 1, 60 parts of SR644 (trade name, polypropylene glycol dimethacrylate: manufactured by Sartomer), 30 parts of isobornyl acrylate, N-isopropylacrylamide as dropping solution (a-6) Example, except that 10 parts of New Coal 707-SFC (trade name, polyoxyethylene polycyclic phenyl ether sulfate: Nippon Emulsifier Co., Ltd.) and 100 parts of deionized water were used as the emulsifier. 1 was used to obtain an impact absorber [6].

Example 7
60 parts of APG-400 (trade name, polypropylene glycol diacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.) as a dropping solution (a-7) instead of the dropping solution (a-1) of Example 1, 30 parts of dicyclopentanyl methacrylate , An emulsion composed of 10 parts of 2-hydroxyethyl methacrylate, 13 parts of Newcol 707-SFC (trade name, polyoxyethylene polycyclic phenyl ether sulfate: manufactured by Nippon Emulsifier Co., Ltd.) and 100 parts of deionized water is used as an emulsifier. Except for the above, shock absorber [7] was obtained in the same manner as in Example 1.

Example 8
70 parts of Bremer PDP-400N (trade name, polypropylene glycol dimethacrylate manufactured by NOF Corporation), 20 parts of adamantyl methacrylate, reactivity as the drop solution (a-8) instead of the drop solution (a-1) of Example 1 The emulsifier was used except that an emulsion comprising 10 parts of Antox MS-60 (trade name, bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate: Nippon Emulsifier Co., Ltd.) and 100 parts of deionized water was used. A shock absorber [8] was obtained in the same manner as in Example 1.

Example 9
Instead of the dropping solution (a-1) of Example 1, 95 parts of SR644 (trade name, polypropylene glycol dimethacrylate: manufactured by Sartomer) as a dropping solution (a-9), 5 parts of dicyclopentanyl methacrylate, new as an emulsifier By the same method as in Example 1 except that an emulsion composed of 10 parts of Cole 707-SFC (trade name, polyoxyethylene polycyclic phenyl ether sulfate: Nippon Emulsifier Co., Ltd.) and 100 parts of deionized water was used. A shock absorber [9] was obtained.

Example 10
In a 500 ml reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 110 parts of deionized water, New Coal 723-SF (trade name, polyoxyethylene polycyclic phenyl ether sulfate salt) : Nippon Emulsifier Co., Ltd.) 2 parts. Thereafter, the internal temperature was raised to 83 ° C. while stirring under a nitrogen gas stream. To the dropping funnel, 10 parts of APG-400 (trade name, polypropylene glycol diacrylate: Shin-Nakamura Chemical Co., Ltd.) as a dropping solution (a-10), 90 parts of tertiary butyl acrylate, Newcor 723-SF (trade name) as an emulsifier , Polyoxyethylene polycyclic phenyl ether sulfate ester salt: manufactured by Nippon Emulsifier Co., Ltd.) and an emulsion comprising 100 parts of deionized water were charged. Next, the monomer emulsion was uniformly added dropwise over 2 hours while maintaining the internal temperature of the reaction vessel at 83 ° C. At the same time, 50.5 parts of 1% aqueous potassium persulfate solution was uniformly added dropwise over 2 hours. After completion of dropping, the reaction was terminated after aging at 83 ° C. for 2 hours. The reaction product was cooled and then filtered through a 400-mesh stainless wire mesh, and the solid content was adjusted to 20% with deionized water to obtain an impact absorber [10].

Example 11
In a 500 ml reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 110 parts of deionized water, New Coal 707-SF (trade name, polyoxyethylene polycyclic phenyl ether sulfate salt) : Nippon Emulsifier Co., Ltd.) 2 parts. Thereafter, the internal temperature was raised to 83 ° C. while stirring under a nitrogen gas stream. To the dropping funnel, 25 parts of Bremer PDP-400N (trade name, polypropylene glycol dimethacrylate: manufactured by NOF Corporation) as a drop solution (a-11), FA-023M (trade name, ethoxylate polypropylene glycol dimethacrylate: Hitachi Chemical Co., Ltd.) Manufactured) 25 parts, 50 parts of styrene, New Coal 707-SF (trade name, polyoxyethylene polycyclic phenyl ether sulfate: manufactured by Nippon Emulsifier Co., Ltd.) as an emulsifier and 100 parts of deionized water are charged. It is. Next, the monomer emulsion was uniformly added dropwise over 2 hours while maintaining the internal temperature of the reaction vessel at 83 ° C. At the same time, 50.5 parts of 1% aqueous potassium persulfate solution was uniformly added dropwise over 2 hours. After completion of dropping, the reaction was terminated after aging at 83 ° C. for 2 hours. The reaction product was cooled and then filtered through a 400 mesh stainless steel wire mesh, and the solid content was adjusted to 20% with deionized water to obtain an impact absorber [11].

Example 12
Instead of the dropping solution (a-11) of Example 11, 100 parts of APG-700 (trade name, polypropylene glycol diacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.) as the dropping solution (a-12) and New Coal 707-SF as the emulsifier (Trade name, polyoxyethylene polycyclic phenyl ether sulfate: manufactured by Nippon Emulsifier Co., Ltd.) Except for using an emulsion composed of 10 parts and 100 parts of deionized water, an impact absorber [ 12] was obtained.

Example 13
In a 500 ml stainless steel container, 200 parts of deionized water, New Coal 707-SFC (trade name, polyoxyethylene polycyclic phenyl ether sulfate: manufactured by Nippon Emulsifier Co., Ltd.) 15 parts, 4% JP-05 (trade name, part) Saponified polyvinyl alcohol: Nihon Vinegar Bipovar Co., Ltd.) 10 parts of an aqueous solution is charged and mixed uniformly. While stirring and mixing with a homogenizer, 13 parts of Blemmer PDT-650 (trade name, polytetramethylene glycol dimethacrylate: NOF Corporation) as a monomer and initiator solution (a-13), 54 parts of isobornyl methacrylate, Blemmer PP -800 (trade name, polypropylene glycol monomethacrylate: NOF Corporation) and 0.5 part of diisononanoyl peroxide were added and dispersed at 10,000 rpm for 10 minutes to obtain an emulsion. A stirrer for the emulsion treated with the homogenizer
A 500 ml reaction vessel equipped with a reflux condenser, a thermometer, and a nitrogen introduction tube was charged, and replaced with nitrogen gas, and then the temperature was raised to 70 ° C. to initiate the reaction. After maintaining the reaction temperature at 70 ° C. for 2 hours, the reaction was further terminated at 80 ° C. for 1 hour and at 90 ° C. for 1 hour. The reaction product was cooled and then filtered through a 400-mesh stainless wire mesh, and the solid content was adjusted to 20% with deionized water to obtain an impact absorber [13].

Example 14
Instead of the monomer and initiator solution (a-13) of Example 13, 50 parts of CN9004 (trade name, aliphatic urethane diacrylate: manufactured by Sartomer) and 49 parts of benzyl methacrylate as the monomer and initiator solution (a-14) Except for using 1 part of ethylene glycol dimethacrylate and 0.5 part of diisononanoyl peroxide, an impact absorber [14] was obtained in the same manner as in Example 13.

Example 15
In place of the monomer and initiator solution (a-13) of Example 13, 50 parts of BAC-45 (trade name, polybutadiene-terminated diacrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd.) as the monomer and initiator solution (a-15), An impact absorber [15] was obtained in the same manner as in Example 13 except that 50 parts of methyl methacrylate and 0.5 parts of diisononanoyl peroxide were used.

Example 16
Instead of the monomer and initiator solution (a-13) of Example 13, 20 parts of TE-2000 (trade name, polybutadiene introduced with methacrylic groups at both ends: Nippon Soda Co., Ltd.) as the monomer and initiator solution (a-16), A shock absorber [16] was obtained in the same manner as in Example 13 except that 80 parts of ethyl methacrylate and 0.5 parts of diisononanoyl peroxide were used.

Example 17
200 parts of solvent naphtha was charged into a 500 ml reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube. Thereafter, the internal temperature was raised to 130 ° C. while stirring under a nitrogen gas stream. In the above dropping funnel, as a dropping solution (a-17), 50 parts of Blemmer PDP-400N (trade name, polypropylene glycol dimethacrylate: NOF Corporation), 50 parts of cyclohexyl methacrylate, 50 parts of solvent naphtha, tertiary-amyl peroxy- A mixture consisting of 10 parts of 2-ethylhexanoate was charged. Next, the above mixture was uniformly added dropwise over 90 minutes while maintaining the internal temperature of the reaction vessel at 130 ° C. After completion of dropping, the reaction temperature was maintained at 130 ° C. for 90 minutes to complete the reaction. The solid content was adjusted to 20% with solvent naphtha to obtain an impact absorber [17]. The polystyrene equivalent Mw of the synthesized copolymer by gel permeation chromatography was 80000.

Example 18
Bremermer PDP-400N (trade name, polypropylene glycol dimethacrylate: manufactured by NOF Corporation) as a dropping solution (a-18) instead of the dropping solution (a-17) of Example 17, 67 parts of isobornyl methacrylate, A shock absorber [18] was obtained in the same manner as in Example 17 except that 50 parts of solvent naphtha and 5.2 parts of tertiary-amylperoxy-2-ethylhexanoate were used. The polystyrene equivalent Mw by the gel permeation chromatograph of the synthesized copolymer was 280000.

Example 19
Instead of the dropping solution (a-17) of Example 17, SR644 (trade name, polypropylene glycol dimethacrylate: manufactured by Sartomer) as a dropping solution (a-19), 25 parts of isobornyl methacrylate, 25 parts of methyl methacrylate , Except that 50 parts of solvent naphtha and 10 parts of tertiary-amyl peroxy-2-ethylhexanoate were used,
A shock absorber [19] was obtained in the same manner as in Example 17. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized copolymer was 60000.

Example 20
Instead of the dropping solution (a-17) of Example 17, as a dropping solution (a-20), CN9004 (trade name, aliphatic urethane diacrylate: manufactured by Sartomer) 50 parts, isobornyl methacrylate 50 parts, solvent naphtha 50 The impact absorber [20] was obtained in the same manner as in Example 17 except that 8 parts of tertiary-amylperoxy-2-ethylhexanoate were used. The polystyrene equivalent Mw of the synthesized copolymer by gel permeation chromatography was 80000.

Example 21
Instead of the dropping solution (a-17) of Example 17, as a dropping solution (a-21), CN9014 (trade name, hydrophobic aliphatic urethane diacrylate: manufactured by Sartomer) 50 parts, methyl methacrylate 50 parts, solvent naphtha 50 The impact absorber [21] was obtained in the same manner as in Example 17, except that 8 parts of tertiary-amylperoxy-2-ethylhexanoate were used. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized copolymer was 90000.

Example 22
Instead of the dropping solution (a-17) of Example 17, 50 parts of BAC-45 (trade name, polybutadiene-terminated diacrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a dropping solution (a-22), 50 parts of methyl methacrylate, solvent Impact absorber [22] was obtained in the same manner as in Example 17 except that 100 parts of naphtha and 16 parts of tertiary-amylperoxy-2-ethylhexanoate were used. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized copolymer was 340000.

Example 23
Instead of the dropping solution (a-17) of Example 17, 50 parts of BAC-45 (trade name, polybutadiene-terminated diacrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a dropping solution (a-23), 50 parts of benzyl methacrylate, solvent Impact absorber [23] was obtained in the same manner as in Example 17 except that 100 parts of naphtha and 16 parts of tertiary-amylperoxy-2-ethylhexanoate were used. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized copolymer was 180,000.

Example 24
Instead of the dropping solution (a-17) of Example 17, 45 parts of BAC-45 (trade name, polybutadiene-terminated diacrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd.) as the dropping solution (a-24), 45 parts of methyl methacrylate, 2 -Shock absorber [24] was obtained in the same manner as in Example 17 except that 10 parts of hydroxyethyl methacrylate, 100 parts of solvent naphtha and 16 parts of tertiary-amylperoxy-2-ethylhexanoate were used. It was. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized copolymer was 120,000.

Example 25
Instead of the dropping solution (a-17) of Example 17, as a dropping solution (a-25), CN9004 (trade name, aliphatic urethane diacrylate: manufactured by Sartomer) 50 parts, methyl methacrylate 50 parts, solvent naphtha 100 parts, A shock absorber [25] was obtained in the same manner as in Example 17 except that 4 parts of tertiary-amylperoxy-2-ethylhexanoate was used. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized copolymer was 250,000.

Example 26
Instead of the dropping solution (a-17) of Example 17, 45 parts of BAC-45 (trade name, polybutadiene-terminated diacrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd.) as the dropping solution (a-26), 45 parts of methyl methacrylate, N -Shock absorber [26] was obtained in the same manner as in Example 17 except that 10 parts of isopropylacrylamide, 100 parts of solvent naphtha, and 16 parts of tertiary-amylperoxy-2-ethylhexanoate were used. . Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized copolymer was 380000.

Example 27
Instead of the dropping solution (a-17) of Example 17, 50 parts of CN9014 (trade name, hydrophobic aliphatic urethane diacrylate: manufactured by Sartomer), 50 parts of styrene, 100 parts of solvent naphtha as the dropping solution (a-27) In the same manner as in Example 17, except that 10 parts of tertiary-amylperoxy-2-ethylhexanoate was used, an impact absorber [27] was obtained. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized copolymer was 40000.

Comparative Example 1
In a 500 ml reaction vessel equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, 180 parts of deionized water and 16 parts of Lebenol WX (trade name, sodium polyoxyethylene alkyl ether sulfate: manufactured by Kao Corporation) as an emulsifier 100 parts of methyl methacrylate were charged. Thereafter, the internal temperature was raised to 80 ° C. while stirring under a nitrogen gas stream. A reaction vessel was charged with 30.3 parts of a 1% aqueous solution of ammonium persulfate and aged at 80 ° C. for 2 hours, and the reaction was completed. The reaction product was cooled and then filtered through a 400 mesh stainless steel wire mesh, and the solid content was adjusted to 20% with deionized water to obtain a comparative additive [1]. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized polymer was 900,000.

Comparative Example 2
In a 500 ml reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 110 parts of deionized water, New Coal 707-SF (trade name, polyoxyethylene polycyclic phenyl ether sulfate salt) : Nippon Emulsifier Co., Ltd.) 2 parts. Thereafter, the internal temperature was raised to 83 ° C. while stirring under a nitrogen gas stream. To the dropping funnel, 50 parts of methyl methacrylate as a dropping solution (n-2), 50 parts of Blemmer PDE-200 (trade name, polyethylene glycol dimethacrylate: manufactured by NOF Corporation), and Newcol 707-SF (trade name, poly as an emulsifier) An emulsion consisting of 10 parts of oxyethylene polycyclic phenyl ether sulfate (manufactured by Nippon Emulsifier Co., Ltd.) and 100 parts of deionized water was charged. Next, while maintaining the internal temperature of the reaction vessel at 83 ° C., the above monomer emulsification (the product was uniformly added dropwise over 2 hours. At the same time, 50.5 parts of 1% potassium persulfate aqueous solution was uniformly added over 2 hours. After completion of the dropwise addition, the reaction was terminated after aging at 83 ° C. for 2 hours, and the reaction product was cooled and filtered through a 400 mesh stainless steel wire mesh, and the solid content was adjusted to 20% with deionized water. Additive [2] was obtained.

Comparative Example 3
Instead of dropping solution (n-2) of Comparative Example 2, dropping solution (n-3) APG-400 (trade name, polypropylene glycol diacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.) 10 parts, normal butyl methacrylate 90 parts, emulsifier As in Comparative Example 2 except that an emulsion comprising 10 parts of New Coal 707-SF (trade name, polyoxyethylene polycyclic phenyl ether sulfate ester salt: manufactured by Nippon Emulsifier Co., Ltd.) and 100 parts of deionized water was used. Comparative additive [3] was obtained by the method.

Comparative Example 4
As a drop solution (n-4) instead of the drop solution (n-2) of Comparative Example 2, 70 parts of cyclohexyl methacrylate, 30 parts of Blemmer PME-1000 (trade name, polyethylene glycol monomethacrylate: NOF Corporation), as an emulsifier New Coal 707-SF (trade name, polyoxyethylene polycyclic phenyl ether sulfate: manufactured by Nippon Emulsifier Co., Ltd.) and a method similar to Comparative Example 2 except that an emulsion comprising 100 parts of deionized water was used. Gave comparative additive [4].

Comparative Example 5
NeoRez R-960 (trade name, urethane dispersion: DSM as a comparative example)
Coating Resins) was used.

Comparative Example 6
As a comparative example, A-5210.05 (trade name, styrene butadiene latex: manufactured by Asahi Kasei Chemicals Corporation) was used.

Comparative Example 7
200 parts of solvent naphtha was charged into a 500 ml reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube. Thereafter, the internal temperature was raised to 130 ° C. while stirring under a nitrogen gas stream. 50 parts of BAC-45 (trade name, polybutadiene-terminated diacrylate: manufactured by Osaka Organic Chemical Co., Ltd.), 50 parts of normal butyl methacrylate, 100 parts of solvent naphtha, and tertiary-amyl par as a dropping solution (n-7) in the dropping funnel. A mixture consisting of 13 parts of oxy-2-ethylhexanoate was charged. Next, the above mixture was uniformly added dropwise over 90 minutes while maintaining the internal temperature of the reaction vessel at 130 ° C. After completion of dropping, the reaction temperature was maintained at 130 ° C. for 90 minutes to complete the reaction. The solid content was adjusted to 20% with solvent naphtha to obtain a comparative additive [7]. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized copolymer was 340000.

Comparative Example 8
Instead of the dropping solution (n-7) of Comparative Example 7, 50 parts of methyl methacrylate, 50 parts of Blenmer PDE-200 (trade name, polyethylene glycol dimethacrylate: NOF Corporation) as a dropping solution (n-8), solvent naphtha Comparative additive [8] was obtained in the same manner as in Comparative Example 7, except that 50 parts and 12 parts of tertiary-amylperoxy-2-ethylhexanoate were used. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized copolymer was 400,000.

Comparative Example 9
A 500 ml reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube was charged with 100 parts of solvent naphtha, 100 parts of methyl methacrylate, and 0.12 part of diisononanoyl peroxide. Thereafter, the internal temperature was raised to 78 ° C. while stirring under a nitrogen gas stream. After maintaining the reaction temperature at 78 ° C for 90 minutes, the temperature was raised to 85 ° C. After maintaining the reaction temperature at 85 ° C. for 120 minutes, 0.45 part of diisononanoyl peroxide and 67 parts of solvent naphtha were added dropwise. The temperature was raised to 95 ° C. 60 minutes after the completion of the dropping. After maintaining the reaction temperature at 95 ° C. for 30 minutes, the reaction was terminated. The solid content was adjusted to 20% with solvent naphtha to obtain a comparative additive [9]. Mw of polystyrene conversion by the gel permeation chromatograph of the synthesized polymer was 150,000.

Paint test example
Test example 1 (performance evaluation with water-based paint)
Using the water-soluble polyester resin / melamine curable coating composition having the composition shown in Table 1, performance evaluation of the impact absorbers shown in Examples and Comparative Examples was performed.

  A paint having the composition shown in Table 1 was prepared, and the shock absorbers and comparative additives in Examples 1 to 16 and Comparative Examples 1 to 6 were added in amounts shown in Tables 4 and 5 (based on 100% by mass of the resin solid content of the paint). , By weight of the solid content in the shock absorber) and dispersed with a lab disperser to obtain a coating material for evaluation.

  The above-mentioned paint was applied to a commercially available cationic electrodeposition coating plate with an applicator so that the dry film thickness was 40 μm, allowed to stand at room temperature for 5 minutes, preheated at 80 ° C. for 7 minutes, and then at 155 ° C. for 20 minutes. An evaluation coating plate was produced by baking.

  The impact absorbability, coating film hardness, and coating film appearance of the evaluation coating plate were evaluated, and the results are shown in Tables 4 and 5.

Test example 2 (performance evaluation with solvent-based paint)
Using the solvent-type polyester alkyd resin / melamine curable coating composition having the composition shown in Table 2, performance evaluation of the impact absorbers shown in Examples and Comparative Examples was performed.

  A paint having the formulation shown in Table 2 was prepared, and the impact absorbers obtained from Examples 17 to 27 and Comparative Examples 7 to 9 and comparative additives were added in the amounts shown in Table 6 (100 mass resin solids of the paint). % By weight in the shock absorber) and dispersed with a lab disperser to obtain an evaluation paint.

  The coating material was applied to a commercially available cationic electrodeposition coating plate with an applicator so that the dry film thickness was 40 μm, and baked at 140 ° C. for 30 minutes to prepare an evaluation coating plate.

  The impact absorption, coating film hardness, and coating film appearance of the evaluation coating plate were evaluated, and the results are shown in Table 6.

Test Example 3 (Performance evaluation in a multilayer coating film)
The water-based paint of the composition shown in Table 1 with the addition of the shock absorber as the first layer, the solvent-based paint of the composition shown in Table 2 without the addition of the shock absorber as the second layer, and the shock absorber as the third layer A multilayer coating film formed by applying a solvent-type clear paint shown in Table 3 with no additive was prepared, and performance evaluation of the shock absorbers shown in Examples and Comparative Examples was performed.

  As the first layer, water-based paints having the composition shown in Table 1 were prepared, and the shock absorbers and comparative additives obtained from Examples 3 to 8, 13, 15, and 17 and Comparative Examples 2, 3, and 11 The coating composition was added in the amount shown in No. 7 (mass% of solid content in the shock absorber with respect to 100% by mass of resin solid content of the paint), and dispersed with a lab disperser to obtain an evaluation paint.

  The above-mentioned evaluation paint was applied to a commercially available cationic electrodeposition coated plate with an applicator so that the dry film thickness was 30 μm, allowed to stand at room temperature for 5 minutes, preheated at 80 ° C. for 7 minutes, and then heated at 155 ° C. for 20 minutes. Baked for a minute.

  As the second layer, a solvent-based paint having the composition shown in Table 2 was prepared, and applied to the test plate coated with the first layer with a wire coater so that the dry film thickness was 15 μm. Forced drying was performed for 10 minutes.

  As the third layer, a clear paint having the composition shown in Table 3 was prepared. The test plate coated with the second layer was coated with a wire coater so that the dry film thickness was 30 μm, and the coating thickness was 30 at 140 ° C. An evaluation coating plate was prepared by baking for a minute.

  The impact absorbability, coating film hardness, and coating film appearance of the evaluation coating plate were evaluated, and the results are shown in Table 7.

The evaluation methods for various additives shown in the test examples are shown below.
(1) Evaluation of impact absorbability Test panels coated in Test Examples 1 to 3 were stored for 1 hour or longer in a freezer adjusted to an internal temperature of -28 ° C. Next, a 2 m high polyvinyl chloride pipe (inner diameter: 2 cm) is placed 10 cm away from the ground, and stands vertically. The test panel taken out of the freezer was placed horizontally just below the pipe. Immediately thereafter, 100 g of M4 nut (200 g in Test Example 3) was dropped onto the coating film through the pipe. The impact absorbability was evaluated by the area of the peeled portion (at a unit area of 100 mm ² ) where the coating film was broken by the nut and the base was exposed.
Excellent shock absorption. (Peeling area 5mm ² or less)
○ Excellent shock absorption. (Peeling area 5mm ² or more, 10mm ² or less)
ΔSlightly inferior in shock absorption. (Peeling area 10 mm ² or more, 15 mm ² or less)
X Impact absorption is inferior. (Peeling area 15mm ² or more)

(2) Coating film hardness The hardness of the obtained coating film was measured using scratch hardness (pencil method) (JIS K5600-5-4) and evaluated as follows.
◎ H or more ○ F
△ HB
× B or less

(3) Coating film appearance The appearance, smoothness, and gloss of the surface of the coating film were visually evaluated as follows.
◎ Equivalent to additive-free coating. (Appearance, smoothness deterioration, gloss reduction is not seen)
○ Slightly inferior to the additive-free coating. (Appearance, smoothness deterioration, gloss reduction is not so much)
△ Inferior to additive-free coating. (Appearance, smoothness deterioration, gloss reduction is slightly seen)
* It is greatly inferior to an additive-free coating film. (Exterior appearance, smoothness deterioration, gloss reduction)

Product names in the table are as follows.

BLEMMER PDE-200: Polyethylene glycol dimethacrylate (manufactured by NOF Corporation)
SR644: Polypropylene glycol dimethacrylate (Sartomer)
APG-400: Polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Blemmer PDP-400N: Polypropylene glycol dimethacrylate (manufactured by NOF Corporation)
APG-700: Polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
FA-023M: ethoxylate polypropylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd.)
BLEMMER PDT-650: Polytetramethylene glycol dimethacrylate (manufactured by NOF Corporation)
CN9004: Aliphatic urethane diacrylate (manufactured by Sartomer)
CN9014: Hydrophobic aliphatic urethane diacrylate (manufactured by Sartomer)
TE-2000: methacrylic group-introduced polybutadiene urethane bond type (manufactured by Nippon Soda Co., Ltd.)
BAC-45: Polybutadiene diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
BLEMMER PP-800: Polypropylene glycol monomethacrylate (manufactured by NOF Corporation)
BLEMMER PME-1000: Polyethylene glycol monomethacrylate (manufactured by NOF Corporation) Antox MS-60: Bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate (manufactured by Nippon Emulsifier Co., Ltd.)

Claims (7)

  10 to 100 parts by mass of at least one macromonomer (A) selected from diacrylate and dimethacrylate macromonomers having a glass transition temperature Tg of 0 ° C. or lower and −80 ° C. or higher, and a homopolymer Glass transition temperature Tg of 40 ° C. or more and 250 ° C. or less, and at least one monomer (B) selected from acrylates, methacrylates, and styrenes having a linear, branched or cyclic hydrocarbon group having C1-C18 carbon atoms A shock absorber which comprises a copolymer obtained by polymerizing 100 parts by weight of a monomer mixture consisting of 0 to 90 parts by weight and which is added to the coating composition to improve the impact resistance of the coating film.   At least one macromonomer (A) selected from diacrylate and dimethacrylate macromonomer having a glass transition temperature Tg of 0 ° C. or lower and −80 ° C. or higher, and a glass transition temperature Tg of 40 ° C. or higher when used as a homopolymer. And at least one monomer (B) selected from acrylates, methacrylates and styrenes having a linear, branched or cyclic hydrocarbon group having a carbon number of C1-C18 and other polymerizable unsaturated monomers A monomer mixture comprising at least one polymerizable unsaturated monomer (C) selected from the group consisting of 10 to 100 parts by mass of the macromonomer (A) and 0 to 90 parts by mass of the monomer (B). And polymer containing 50 parts by mass or less of the monomer (C) per 100 parts by mass of the mixture Comprises a copolymer obtained Te, shock absorbers to improve the impact resistance of the coating film by adding to the coating composition.   The number average molecular weight of diacrylate and dimethacrylate macromonomer (A) is 400 or more and 15000 or less, which is added to the coating composition according to claim 1 or 2 to improve the impact resistance of the coating film. Shock absorber to make.   The coating composition which contains 1-20 mass% in conversion of solid content with respect to the resin solid content of 100 mass% contained in a coating material in any one of Claims 1-3.   A coating film, wherein the coating composition according to claim 4 is formed by being applied to a substrate and cured.   A method for forming a multilayer coating film, comprising: applying a top coating to the entire surface or a part of the coating film according to claim 5.   A multilayer coating film obtained by the method according to claim 6.