JP2011153204A - Urethane-modified acrylic resin, and coating agent and adhesive produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin usable as an adhesive and a coating agent having excellent weather resistance and water resistance while keeping adhesiveness of an ultraviolet curable or electron radiation curable coating film to a plastic sheet, and to provide an adhesive and a coating agent produced by using the resin. <P>SOLUTION: The urethane-modified acrylic resin is produced by urethanization reaction of (A) an acrylic polyol having an alicyclic skeleton, a hydroxyl value of 5-35 mgKOH/g and a weight-average molecular weight of 5,000-30,000, (B) a polyol except the acrylic polyol and having an alicyclic skeleton and (C) an organic diisocyanate, wherein the mass ratio (A)/(B) of the acrylic polyol (A) to the polyol (B) is 30/70 to 70/30. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a design sheet used for interior and exterior of buildings, interior and exterior of vehicles, computers and portable terminals, and a plastic sheet (polypropylene, PET, etc.) as a base material and an ultraviolet curable coating film or electron beam as a top coat. The present invention relates to a polyurethane-modified acrylic resin used for bonding a curable coating film, and an adhesive and a coating agent using the same.

  Designable sheets used for building interiors and exteriors, vehicle interiors and exteriors, computers and mobile terminals are made by applying a UV curable or electron beam curable coating film as a top coat to a plastic sheet as a base material. Since the UV curable or electron beam curable coating film and the plastic sheet are not good in adhesion, a single adhesive layer is provided between them. At present, the adhesive used in the adhesive layer mainly contains an ultraviolet absorber and a light stabilizer from the viewpoint of weather resistance (for example, Patent Document 1).

JP 2003-053908 A

  However, there are still many problems in weather resistance, and compatibility with adhesion is required. Therefore, the present invention uses a resin that can be used for an adhesive and a coating agent having excellent weather resistance and water resistance while maintaining the adhesion between the ultraviolet curable or electron beam curable coating film and the plastic sheet, and the same. It is an object to provide an adhesive and a coating agent.

  As a result of intensive studies by the present inventors, urethanization reaction of an acrylic polyol having an alicyclic skeleton and specific properties, an alicyclic skeleton, a polyol other than the acrylic polyol, and an organic diisocyanate The urethane-modified acrylic resin obtained by doing so has been found to be a means for solving the above problems.

  That is, the present invention comprises (1) an acrylic polyol (A) having an alicyclic skeleton, a hydroxyl value of 5 to 35 mg KOH / g, and a weight average molecular weight of 5000 to 30000, an alicyclic skeleton, and other than the acrylic polyol. A urethane-modified acrylic resin obtained by subjecting a polyol (B) and an organic diisocyanate (C) to a urethanization reaction, wherein the mass ratio of the polyol (B) to the acrylic polyol (A) (A) / (B ) Is a urethane-modified acrylic resin having a ratio of 30/70 to 70/30.

  The present invention also relates to (2) the urethane-modified acrylic resin according to (1), wherein the polyol (B) is a polyester polyol and / or a polycarbonate diol.

  The present invention also relates to (3) a coating agent comprising the urethane-modified acrylic resin according to (1) or (2).

  The present invention also relates to (4) an adhesive containing the urethane-modified acrylic resin according to (1) or (2).

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive agent and coating agent which have the outstanding weather resistance and water resistance can be provided, maintaining the adhesiveness of an ultraviolet curable type or electron beam curable coating film, and a plastic sheet.

  The urethane-modified acrylic resin of the present invention has an alicyclic skeleton, an acrylic polyol (A) having a hydroxyl value of 5 to 35 mgKOH / g and a weight average molecular weight of 5,000 to 30,000, an alicyclic skeleton, and other than the acrylic polyol. The urethane-modified acrylic resin obtained by subjecting the polyol (B) and the organic diisocyanate (C) to a urethanation reaction, the mass ratio (A) / (of the polyol (B) to the acrylic polyol (A) B) is a urethane-modified acrylic resin having a ratio of 30/70 to 70/30.

  Hereinafter, the raw material used for the urethane-modified acrylic resin of the present invention will be described.

Acrylic polyol (A)
The acrylic polyol (A) used for the urethane-modified acrylic resin of the present invention has an alicyclic skeleton, has a hydroxyl value of 5 to 35 mgKOH / g, and a weight average molecular weight of 5000 to 30000.

  The hydroxyl value is preferably 6 to 30 mgKOH / g, and more preferably 8 to 25 mgKOH / g. When the hydroxyl value is less than 5 mgKOH / g, the resulting urethane-modified acrylic resin becomes cloudy and is inferior in weather resistance, water resistance and adhesion. On the other hand, if it exceeds 35 mgKOH / g, gelation will occur. Examples of a method for setting the hydroxyl value within the above range include copolymerizing a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. Although it is appropriately selected depending on the composition, the target hydroxyl value, etc., a copolymer obtained by copolymerizing about 1 to 10 parts by mass of a hydroxyl group-containing monomer with respect to 100 parts by mass of the total mass of all monomers constituting the acrylic resin. Can do. For example, in the case of 2-hydroxyethyl (meth) acrylate, 2-7 parts by mass of 2-hydroxyethyl methacrylate is copolymerized with respect to 100 parts by mass of the total mass of all monomers constituting the acrylic resin. It is done. The hydroxyl value can be determined by a titration method.

  The weight average molecular weight is preferably 8000 to 20000, and more preferably 10,000 to 15,000. When the weight average molecular weight is less than 5000, the strength of the coating film is inferior, and when it exceeds 30000, gelation occurs. Examples of the method for setting the weight average molecular weight within the above range include adjusting the addition amount of a polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, About 0.001 to 10 parts by mass of a polymerization initiator can be added to 100 parts by mass of the total mass of all monomers.

For example, in the case of azobisisobutyronitrile, 1.5 to 3.0 parts of azobisisobutyronitrile may be used with respect to 100 parts by mass of the total mass of all monomers constituting the acrylic resin. . In addition, a weight average molecular weight is a polystyrene conversion value using the calibration curve by a standard polystyrene by the gel permeation chromatography method (GPC).

  In the present invention, since the acrylic polyol has an alicyclic skeleton, the water resistance is improved, so that the weather resistance is excellent.

The acrylic polyol can be obtained by copolymerizing a monomer component containing an alicyclic skeleton-containing unsaturated monomer and a hydroxyl group-containing unsaturated monomer. As the alicyclic skeleton-containing unsaturated monomer, for example, an unsaturated monomer represented by the following general formula (I) is preferably used. In addition, only 1 type may be used for an alicyclic skeleton containing unsaturated monomer, and it may use 2 or more types together.

In the general formula (I), R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an ester group having a cycloalkyl structure having 3 to 36 carbon atoms which may have a substituent. . In the general formula (I), the substituent in the cycloalkyl structure which may have a substituent of the ester group represented by R ² is not particularly limited, but for example, a hydrocarbon group having 1 to 18 carbon atoms Etc. Further, the cycloalkyl structure in the cycloalkyl structure which may have a substituent of the ester group represented by R ² is not particularly limited, and examples thereof include a cyclobutyl structure, a cyclopentyl structure, a cyclohexyl structure, a cyclobutyl structure, and a cyclooctyl. Structure, cyclononyl structure, cyclodecyl structure, cycloundecyl structure, cyclododecyl structure, cyclotridecyl structure, cyclotetradecyl structure, cyclopentadecyl structure, cyclohexadecyl structure, cycloheptadecyl structure, cyclooctadecyl structure, isobornyl structure, di Examples thereof include a cyclopentaniel structure.

  Examples of the alicyclic skeleton-containing unsaturated monomer represented by the general formula (I) include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentaniel (meth) acrylate, (meth) Methylcyclohexyl acrylate, tert-butylcyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclododecyl (meth) acrylate, 4-methylolcyclohexyl (meth) acrylate, 4-methylcyclohexyl (meth) acrylate Etc. These alicyclic skeleton containing unsaturated monomers may use only 1 type, and may use 2 or more types together. Of these, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentaniel (meth) acrylate are preferably used. Here, (meth) acrylic acid means either acrylic acid or methacrylic acid.

  The proportion of the alicyclic skeleton-containing unsaturated monomer in the monomer component is preferably 5 parts by mass or more, more preferably 10 to 30 parts by mass, and particularly preferably 15 to 25 parts by mass in a total of 100 parts by mass of monomers. is there. When the ratio of the alicyclic skeleton-containing unsaturated monomer is less than 5 parts by mass, there is a tendency that a problem occurs in rigidity.

  The hydroxyl group-containing unsaturated monomer is not particularly limited, and examples thereof include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone-modified hydroxy (meth) acrylate. It is done. These hydroxyl group-containing unsaturated monomers may be used alone or in combination of two or more.

  The proportion of the hydroxyl group-containing unsaturated monomer in the monomer component is preferably 1 to 10 parts by mass, more preferably 2 to 7 parts by mass, in a total of 100 parts by mass of monomers. When the hydroxyl group-containing unsaturated monomer is less than 1 part by mass, there is a tendency for compatibility to occur, and when it exceeds 10 parts by mass, there is a tendency for rigidity to occur. In the present invention, a monomer having both an alicyclic skeleton structure and a hydroxyl group may be used as the alicyclic skeleton-containing unsaturated monomer and the hydroxyl group-containing unsaturated monomer. The amount of the monomer having both the structure and the hydroxyl group is considered as the amount of each of the alicyclic skeleton-containing unsaturated monomer and the hydroxyl group-containing unsaturated monomer. That is, the mass of the monomer having both the alicyclic skeleton structure and the hydroxyl group is counted as the mass of the alicyclic skeleton-containing unsaturated monomer in the monomer component, and at the same time, It is also counted as the mass of the saturated monomer.

  As a monomer for obtaining the acrylic polyol, in addition to the alicyclic skeleton-containing unsaturated monomer and the hydroxyl group-containing unsaturated monomer, other polymerizable monomers copolymerizable therewith may be contained. Although it does not specifically limit as another polymerizable monomer which can be copolymerized, For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate , N-octyl (meth) acrylate, isooctyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, 2-acetoacetoxyethyl (Meth) acrylic acid esters such as acrylate and 2-acetoacetoxyethyl methacrylate; (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, carboxyl group terminal caprolactone modified acrylate, carboxyl group terminal caprolactone modified methacrylate, Unsaturated monomers having an acidic functional group such as sulfoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate; vinyl acetate, vinyl butyrate, vinyl caproate, Vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, vinyl octylate, monochloro vinyl acetate Vinyl esters such as vinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate; vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ- Polymerizable unsaturated monomers having silicon atoms such as methacryloxypropyltrimethoxysilane and trimethylsiloxyethyl methacrylate; trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadodecafluoro Decyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate, hexafluoropropyl methacrylate, tribromophenol 3EO addition methacrylate Polymerizable unsaturated monomers having a halogen atom such as benzoate, perfluorooctylethyl (meth) acrylate; (meth) acrylamide, N, N-dimethylaminopropylacrylamide, N-isopropylacrylamide, tert-butylacrylamide, methylenebis (meta ) Acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl acrylamide, N-methylol (meth) acrylamide, N, N′-dimethylaminoethyl (meth) acrylate, N, N′-diethylaminoethyl ( (Meth) acrylate, N-methyl-N-vinylformamide, methacryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl methacrylate sulfate, morpholine EO Polymerizable unsaturated monomers having nitrogen atoms such as methacrylates, N-vinylmethyl carbemate, N, N′-methylvinylacetamide, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate quaternized product, diacetone acrylamide, etc. Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol diacrylate, polyethylene glycol # 200 di (meth) acrylate, polyethylene glycol # 400 di (meth) acrylate, polyethylene glycol # 600 di (meth) Acrylate, polyethylene glycol # 1000 diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol di (meth) acrylate, 1,6-hex Diol di (meth) acrylate, 1,9-nonanediol diacrylate, neopentyl glycol di (meth) acrylate, polypropylene glycol # 400 di (meth) acrylate, EO-modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetra Multifunctional polymerizable unsaturated such as acrylate, dipentaerythritol hexaacrylate, trisacryloyloxyethyl phosphate, glycerin dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane diacrylate, trimethylolpropane tri (meth) acrylate Monomer: Vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl n-propyl ether, vinyl Ruisobutyl ether, vinyl-n-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-2-ethylhexyl ether, vinyl-n-octadecyl ether, cyanomethyl vinyl ether, 2,2-dimethylaminoethyl vinyl ether, 2- Vinyl ethers such as chloroethyl vinyl ether, β-difluoromethyl vinyl ether, divinyl ether, divinyl acetal; polymerizable unsaturated monomers having an isocyanate group such as 2-methacryloyloxyethyl isocyanate, methacryloyl isocyanate; vinyl chloride, vinylidene chloride, etc. Can be mentioned. Among these, (meth) acrylic acid esters are preferably used. In addition, these may use only 1 type and may use 2 or more types together.

  The proportion of the other polymerizable monomer in the monomer component is not particularly limited as long as it is 80 parts by mass or less in 100 parts by mass of the monomers, and may be set as appropriate.

  The polymerization method for obtaining the acrylic polyol by polymerizing the monomer components is not particularly limited, and for example, a conventionally known polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization or the like may be employed. That's fine. Examples of the solvent that can be used in the polymerization include alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane; aliphatic hydrocarbon solvents such as n-heptane; toluene, xylene Aromatic hydrocarbon solvents such as ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, etc .; acetone, methyl ethyl ketone Ketone solvents such as methyl isobutyl ketone and cyclohexanone; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexanol, ethylene glycol, Alcohol solvents such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-tert-butyl ether, 3-methyl-3-methoxybutanol, dipropylene glycol monomethyl ether; ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether solvents such as ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; tetrahydrofuran, N, N-dimethylformamide, dimethylacetamide, dioxane, chloroform, etc. are used, and these are used alone or in combination. can do. The amount of the solvent used is not particularly limited, and may be appropriately set according to the polymerization reaction.

  In the polymerization, a polymerization initiator can be used as necessary. The polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis- (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, and 2,2′-azobis. Azo initiators such as (2,4-dimethylvaleronitrile); benzoyl peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butylperoxy-2- Usual radical initiators such as peroxide initiators such as ethyl hexanoate and cumene hydroperoxide can be used alone or in combination. In addition, the usage-amount of a polymerization initiator is although it does not restrict | limit in particular, Preferably it is 0.001-10 mass parts with respect to a total of 100 mass parts of the said monomer component.

  In the polymerization, a chain transfer agent can be used as necessary. The chain transfer agent is not particularly limited, and examples thereof include n-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, cetyl mercaptan, stearyl mercaptan, thioglycolic acid, Mercaptans such as thioglycerol, ethylenethioglycol, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, mercaptoglycerin, mercaptosuccinic acid, mercaptopropionic acid; halogen compounds such as carbon tetrachloride, chloroform, trichlorobromoethane, bromoform; Disulfides; secondary alcohols; isopropyl alcohol, dioxane, tetrahydrofuran, isopropyl benzol, α-methylstyrene dimer , 2,4-diphenyl-4-methyl-1-pentene; the like can be used singly or in combination. In addition, although the usage-amount of a chain transfer agent is not restrict | limited in particular, Preferably it is 0.1-10 mass parts with respect to a total of 100 mass parts of the said monomer component.

  The polymerization conditions for the polymerization are not particularly limited and may be appropriately selected. Specifically, the polymerization temperature is preferably 10 to 160 ° C, more preferably 30 to 140 ° C. The polymerization time may be appropriately selected according to the progress of the reaction.

Polyol (B)
The polyol (B) used for the urethane-modified acrylic resin of the present invention is a polyol other than an acrylic polyol having an alicyclic skeleton. Since the polyol (B) has an alicyclic skeleton, the water resistance is improved and the weather resistance is excellent.

  The hydroxyl value of the polyol (B) is preferably 30 to 400 mgKOH / g, more preferably 80 to 280 mgKOH / g, and particularly preferably 100 to 250 mgKOH / g. If the hydroxyl value is less than 30 mgKOH / g, gelation tends to occur, and if it exceeds 400 mgKOH / g, the strength of the coating film tends to be inferior.

  The weight average molecular weight of the polyol (B) is preferably 200 to 5000, more preferably 300 to 2000, and particularly preferably 500 to 1000. When the weight average molecular weight is less than 200 or more than 5000, there is a tendency to cause a problem in rigidity.

  Examples of the polyol (B) include polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols, and silicon polyols having an alicyclic skeleton.

  Examples of the polyether polyol having an alicyclic skeleton include those obtained by ring-opening polymerization of a cyclic ether, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  As the polyester polyol having an alicyclic skeleton, those obtained by performing a known polycondensation reaction of dibasic acid and polyhydric alcohol can be used. The thing in which at least one of a monohydric alcohol contains alicyclic skeleton is used. Examples of the dibasic acid having an alicyclic skeleton include cyclopentane dicarboxylic acid, cyclohexane dicarboxylic acid, cycloheptane dicarboxylic acid, cyclooctane dicarboxylic acid, and a mixture thereof. Examples of the polyhydric alcohol having an alicyclic skeleton include cyclopentanediol, cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and mixtures thereof. As a monomer for obtaining a polyester polyol having an alicyclic skeleton, in addition to the dibasic acid having the alicyclic skeleton and the polyhydric alcohol having the alicyclic skeleton, succinic acid, glutaric acid, adipic acid, pimelin Acid, suberic acid, azelaic acid, sebacic acid, dicarboxylic acid such as phthalic acid or its anhydride, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butane Diol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3 -Hexane glycol, 2,2,4-trimethyl-1,3- Ntanjioru, 3,3-dimethylol heptane, 1,9-nonanediol, 2-methyl-1,8-octanediol, it is possible to use a low molecular weight diol such as bis-hydroxyethoxy benzene.

  Examples of the polyether ester polyol include those obtained by ring-opening polymerization of a cyclic ether to the polyester polyol, and those obtained by polycondensing a polyether polyol and a dicarboxylic acid having an alicyclic skeleton.

  Examples of the polycarbonate polyol include those obtained by transesterification of a diol having an alicyclic skeleton and a dialkyl carbonate. Examples of the diol having an alicyclic skeleton include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 -Cyclohexanedimethanol, 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol are exemplified. These may be used alone or in combination of two or more. Examples of the dialkyl carbonate include dimethyl carbonate and diphenyl carbonate. Among these, dimethyl carbonate is preferable from the viewpoint of reactivity. In addition to the diol having the alicyclic skeleton, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-ethyl-4-butyl-1,3 -Propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol Use polyols such as It is possible.

  Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol.

  Examples of the silicon polyol include polydimethylsiloxane polyol. Moreover, the mixture of these 2 or more types is mentioned.

  In the present invention, the polyol (B) is preferably a polyester polyol and / or a polycarbonate polyol having an alicyclic skeleton, and is synthesized using cyclohexanedimethanol for the reason of achieving both adhesion and water resistance. More preferred are polyester polyols and / or polycarbonate polyols.

  In the present invention, the mass ratio (A) / (B) of the acrylic polyol (A) and the polyol (B) is 30/70 to 70/30, preferably 40/60 to 60/40, more preferably. Is 45/55 to 55/45. When (A) / (B) is less than 30/70, the weather resistance tends to be inferior, and when it exceeds 70/30, the adhesion and the adhesiveness tend to be inferior.

Organic diisocyanate (C)
The organic diisocyanate (C) used in the urethane-modified acrylic resin of the present invention is not particularly limited, and examples thereof include hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate. Aliphatic diisocyanates; cyclophoric diisocyanates such as isophorone diisocyanate (IPDI), 4,4′-methylenebis (cyclohexyl isocyanate) (H12MDI), ω, ω′-diisocyanate dimethylcyclohexane; xylylene diisocyanate, tetramethylxylylene diisocyanate, etc. Aliphatic diisocyanates having aromatic rings; p-phenylene diisocyanate, tolylene diisocyanate (TDI), 4,4'-diphenyl And aromatic diisocyanates such as methane diisocyanate (MDI), naphthalene-1,5-diisocyanate and tolidine diisocyanate; and mixtures of two or more of these. Among these, alicyclic diisocyanates can be most suitably used in consideration of the weather resistance of the urethane-modified acrylic resin.

  It mix | blends so that the isocyanate group of organic diisocyanate may be set to 90/100-99/100 by an equivalent ratio (NCO / OH) with respect to the sum total of the hydroxyl group of acrylic polyol (A) and organic polyol (B). If the equivalent ratio is less than 90/100, the resin tends to become cloudy, and if it exceeds 99/100, the resin tends to gel.

  The urethane-modified acrylic resin of the present invention can be obtained by urethanizing the components (A) to (C). The urethanization reaction is performed by a known method such as a one-shot method or a prepolymerization method. The solvent for the urethanization reaction is not particularly limited as long as it is an inert solvent for the reaction. For example, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate and cellosolve acetate Hydrocarbons such as benzene, toluene, xylene and hexane; chlorides such as methylene chloride and dichloroethane; ethers such as tetrahydrofuran and diethyl ether; aprotic such as dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone Polar solvents; etc. and mixtures of two or more of these are used.

  As a catalyst for producing the urethane-modified acrylic resin, a normal urethanization reaction catalyst can be used. For example, tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate; iron compounds such as iron acetylacetonate and ferric chloride; tertiary amines such as triethylamine and triethylenediamine Compound; and the like.

  The urethanization reaction is performed at 70 to 90 ° C, preferably 75 to 85 ° C for 2 to 4 hours.

The urethane-modified acrylic resin of the present invention is suitable as a component of a coating agent or an adhesive.
The coating agent or adhesive of this invention contains the said urethane modified acrylic resin as a main component, and the density | concentration of a urethane modified acrylic resin is suitably prepared according to the objective.

  The coating agent or adhesive of the present invention includes, as other components, a curing agent, a flame retardant, a plasticizer, an antioxidant, an ultraviolet absorber, a dye, a pigment, a filler, an internal release agent, a reinforcing material, a matting agent, It is used by blending a conductivity imparting agent, a charge control agent, an antistatic agent, a lubricant and the like.

  The adhesive or coating agent of the present invention is usually used after diluted in an organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane; acetone, Ketone solvents such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone; ether solvents such as diethyl ether, 1,4-dioxane and tetrahydrofuran; ethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, propylene Cellosolve solvents such as glycol dimethyl ether and propylene glycol monomethyl ether acetate; monobasic acid ester solvents such as ethyl acetate and butyl acetate; Pin acid, dimethyl succinate, dibasic esters such as dioctyl phthalate; dimethylformamide, dimethylacetamide, N- methylpyrrolidone and the like.

  In the present invention, it is preferable to use an organic disissocyanate as a curing agent since the coating strength and durability are improved. As the organic diisocyanate, the same ones as described above are used. The compounding quantity of organic diisocyanate is 0.5-10 mass parts in conversion of solid content with respect to 100 mass parts of urethane-modified acrylic resins.

  The coating agent or adhesive of the present invention can be applied to various substrates. Examples of the base material include inorganic base materials such as glass, slate, concrete, and mortar; aluminum, iron, zinc, tin, copper, titanium, stainless steel, tinplate, tin, and metal plated with zinc, tin, chromium, etc. on the surface , Metal base materials such as metal whose surface is treated with chromic acid or phosphoric acid; polyethylene resin, polypropylene resin, polyvinyl chloride resin, ABS (acrylonitrile-butadiene-styrene) resin, FRP (fiber reinforced plastic), polycarbonate resin, Examples thereof include plastic base materials such as polymethyl methacrylate, polystyrene resin, polyester resin, acrylic resin, epoxy resin, and nylon resin; wood such as cypress, cedar, pine, and plywood; organic base material such as paper.

  Hereinafter, although the specific example of this invention is given, this invention is not limited to this.

<Example 1>
100 parts by mass of methyl isobutyl ketone as a solvent was charged in a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, and the temperature was raised to 110 ° C. In this solvent, 74.5 parts by mass of methyl methacrylate, 5.5 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of cyclohexyl methacrylate, and 2.0 parts by mass of azobisisobutyronitrile as a polymerization initiator were mixed. The solution was added dropwise over 2 hours. Thereafter, the mixture was kept at 110 ° C. for 2 hours and diluted with 50 parts by mass of methyl isobutyl ketone to synthesize acrylic polyol (A1). When the hydroxyl value of the obtained acrylic polyol (A1) was measured by a titration method, it was 23.7 mgKOH / g. As a result of measuring the weight average molecular weight using GPC, it was 12000 in terms of polystyrene. The GPC conditions are shown below.

<GPC conditions>
Equipment used: Tosoh Corporation, HCL-8320
Column: manufactured by Tosoh Corporation, TSK gel SuperMultipore HZ-H
Eluent: Tetrahydrofuran (THF)
To 100 parts by mass of this acrylic polyol (A1), 100 parts by mass of FLEXOREZ188 (polyester polyol mainly composed of adipic acid and polyhydric alcohol, manufactured by King Industries, hydroxyl value 230 mgKOH / g) and urethanization catalyst (dibutyltin dilaurate) 0.2 parts by mass was added and the temperature was raised to 80 ° C. Next, 46 parts by mass of isophorone diisocyanate was added dropwise over 30 minutes, and the mixture was kept at 80 ° C. for 2 hours. Dilution with 200 parts by mass of methyl isobutyl ketone gave urethane-modified acrylic resin (I).

<Example 2>
Example 1 except that 78.0 parts by weight of methyl methacrylate, 2.0 parts by weight of 2-hydroxyethyl methacrylate, 20 parts by weight of cyclohexyl methacrylate and 2.0 parts by weight of azobisisobutyronitrile were used. To obtain an acrylic polyol (A2) having a hydroxyl value of 8.6 mgKOH / g and a weight average molecular weight of 12,000. Using the obtained acrylic polyol (A2), the urethane-modified acrylic resin (II) was synthesized by urethanation reaction in the same manner as in Example 1.

<Example 3>
Example 1 except that 73.0 parts by weight of methyl methacrylate, 7.0 parts by weight of 2-hydroxyethyl methacrylate, 20 parts by weight of cyclohexyl methacrylate, and 2.0 parts by weight of azobisisobutyronitrile were used. To obtain an acrylic polyol (A3) having a hydroxyl value of 30.2 mgKOH / g and a weight average molecular weight of 12,000. Using the obtained acrylic polyol (A3), the urethane-modified acrylic resin (III) was synthesized by urethanation reaction in the same manner as in Example 1.

<Example 4>
An acrylic polyol (A4) having a hydroxyl value of 23.7 mgKOH / g and a weight average molecular weight of 7000 was obtained in the same manner as in Example 1 except that 3 parts of azobisisobutyronitrile was used. Using the obtained acrylic polyol (A4), the urethane-modified acrylic resin (IV) was synthesized by urethanation reaction in the same manner as in Example 1.

<Example 5>
An acrylic polyol (A5) having a hydroxyl value of 23.7 mgKOH / g and a weight average molecular weight of 28000 was obtained in the same manner as in Example 1 except that 0.5 part of azobisisobutyronitrile was used. Using the obtained acrylic polyol (A5), the urethane-modified acrylic resin (V) was synthesized by urethanation reaction in the same manner as in Example 1.

<Example 6>
In the same manner as in Example 1, an acrylic polyol (A1) having a hydroxyl value of 23.7 mgKOH / g and a weight average molecular weight of 12,000 was obtained. It was synthesized from 100 parts by weight of the obtained acrylic polyol (A1) from UM90 (1/3) (1,6-hexanediol / 1,4-dimethanolcyclohexane (= 1/3 (molar ratio)) and dimethyl carbonate. Polycarbonate diol having a molecular weight of about 900, 100 parts by mass of Ube Industries, Ltd., hydroxyl value 115 mgKOH / g) and 0.2 parts by mass of urethanization catalyst (dibutyltin dilaurate) were added, and the temperature was raised to 80 ° C. 24 parts by mass of isophorone diisocyanate was added dropwise over 30 minutes, and the mixture was kept at 80 ° C. for 2 hours. Diluted with 200 parts by mass of methyl isobutyl ketone to synthesize urethane-modified acrylic resin (VI).

<Example 7>
Urethane-modified acrylic resin (VII) was synthesized in the same manner as in Example 6 except that the polycarbonate diol UM90 (1/3) was 150 parts by mass and isophorone diisocyanate was 34 parts by mass.

<Example 8>
A urethane-modified acrylic resin (VIII) was synthesized in the same manner as in Example 6 except that 66 parts by mass of UM90 (1/3) which is a polycarbonate diol and 18 parts by mass of isophorone diisocyanate were used.

<Comparative Example 1>
100 parts by mass of methyl isobutyl ketone as a solvent was charged in a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, and the temperature was raised to 110 ° C. In this solvent, 79.0 parts by mass of methyl methacrylate, 1.0 part by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of cyclohexyl methacrylate and 2.0 parts by mass of azobisisobutyronitrile as a polymerization initiator were mixed. The solution was added dropwise over 2 hours. Thereafter, the mixture was kept at 110 ° C. for 2 hours and diluted with 50 parts by mass of methyl isobutyl ketone to synthesize acrylic polyol (a1). The obtained acrylic polyol (a1) had a hydroxyl value of 4.3 mgKOH / g and a weight average molecular weight of 12,000.

  100 parts by mass of this acrylic polyol (a1) and 100 parts by mass of FLEXOREZ188 (polyester polyol mainly composed of adipic acid and polyhydric alcohol, manufactured by King Industries, hydroxyl value 230 mgKOH / g) and urethanization catalyst (dibutyltin dilaurate) 0 .2 parts by mass was added and the temperature was raised to 80 ° C. 46 parts by mass of isophorone diisocyanate was added dropwise over 30 minutes, and the mixture was kept at 80 ° C. for 2 hours. Diluted with 200 parts by mass of methyl isobutyl ketone to synthesize urethane-modified acrylic resin (IX). The obtained urethane-modified acrylic resin (IX) was cloudy.

<Comparative example 2>
Comparative Example 1 except that 71.0 parts by weight of methyl methacrylate, 9.0 parts by weight of 2-hydroxyethyl methacrylate, 20 parts by weight of cyclohexyl methacrylate, and 2.0 parts by weight of azobisisobutyronitrile were used. To obtain an acrylic polyol (a2) having a hydroxyl value of 38.8 mgKOH / g and a weight average molecular weight of 12,000. Using the obtained acrylic polyol (a2), the urethane-modified acrylic resin (X) was synthesized by urethanization reaction as in Comparative Example 1. The obtained urethane-modified acrylic resin (X) was gelled.

<Comparative Example 3>
An acrylic polyol (a3) having a hydroxyl value of 23.7 mgKOH / g and a weight average molecular weight of 33000 was obtained in the same manner as in Example 1 except that 0.3 part of azobisisobutyronitrile was used. Using the obtained acrylic polyol (a3), the urethane-modified acrylic resin (XI) was synthesized by urethanization reaction in the same manner as in Example 1. The obtained urethane-modified acrylic resin (XI) was gelled.

<Comparative example 4>
The hydroxyl value was determined in the same manner as in Comparative Example 1 except that 98.0 parts by weight of methyl methacrylate, 2.0 parts by weight of 2-hydroxyethyl methacrylate, and 2.0 parts by weight of azobisisobutyronitrile were used. An acryl polyol (a4) having an alicyclic skeleton of 8.6 mg KOH / g and a weight average molecular weight of 12,000 was obtained. Using the obtained acrylic polyol (a4), the urethane-modified acrylic resin (XII) was synthesized by urethanation in the same manner as in Comparative Example 1.

<Comparative Example 5>
Instead of FLEXOREZ188, Kurapol P510 (3-methyl-1,5-pentanediol adipate, polyester polyol, manufactured by Kuraray Co., Ltd., hydroxyl value 230 mgKOH / g) was used as a polyol having no alicyclic skeleton. In the same manner as in Example 1, urethane-modified acrylic resin (XIII) was synthesized.

<Comparative Example 6>
A urethane-modified acrylic resin (XIV) was synthesized in the same manner as in Example 6 except that 25 parts by mass of UM90 (1/3) which is a polycarbonate diol and 10.5 parts by mass of isophorone diisocyanate were used.

  The polyols used in the above examples and comparative examples are represented by the following formulas (II) to (IV).

FLEXOREZ188 (polyester polyol mainly composed of adipic acid and polyhydric alcohol, manufactured by King Industries, hydroxyl value 230 mgKOH / g)

  In formula (II), n represents an integer of 1 or more.

Kurapol P510 (3-methyl-1,5-pentanediol adipate, polyester polyol, manufactured by Kuraray Co., Ltd., hydroxyl value 230 mgKOH / g)

  In formula (III), n represents an integer of 1 or more.

A polycarbonate diol having a molecular weight of about 900 synthesized from UM90 (1/3) (1,6-hexanediol / 1,4-dimethanolcyclohexane (= 1/3 (molar ratio)) and dimethyl carbonate, manufactured by Ube Industries, (Hydroxyl value 115mgKOH / g)

In the formula (IV), R is

Or a hexylene group. n shows 3-6.

  The urethane-modified acrylic resins (I) to (XIV) obtained in the examples and comparative examples were evaluated as follows. However, the urethane-modified acrylic resins (IX) and (X) were gelled and could not be evaluated.

(1) Residue on heating 1.5 g of urethane-modified acrylic resin obtained in a metal petri dish was collected and dried at 108 ° C. for 3 hours, and the weights before and after drying were compared. The results are shown in Tables 1-3.
(2) Viscosity The viscosity was measured with an E-type viscometer at 25 ° C. and 1010 rpm. The results are shown in Tables 1-3.
(3) Weight average molecular weight The weight average molecular weight was measured on condition of the following. The results are shown in Tables 1-3.
<GPC conditions>
Equipment used: Tosoh Corporation, HCL-8320
Column: manufactured by Tosoh Corporation, TSK gel SuperMultipore HZ-H
Eluent: Tetrahydrofuran (THF)
(4) Weather resistance test Urethane-modified acrylic obtained in Examples and Comparative Examples on PET film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd., hereinafter referred to as “treated PET film”) with one surface subjected to easy adhesion treatment. After coating the resin with a film thickness of 10 μm, it was dried at 50 ° C. for 30 minutes to prepare a test piece. The test piece was irradiated with a sunshine weather meter (Suga Test Instruments Co., Ltd., Sunshine Weather Meter S80) for 1000 hours. After irradiation, the test piece is cross-cut into 2 mm wide squares, 100 squares are made, cellotape (registered trademark) is applied to these squares, and the coating is peeled off at an angle of 90 degrees. The presence or absence was confirmed visually. About 100 squares, the case where peeling was zero was set to “◯”, and the case where it was 1 or more was set to “x”. The results are shown in Tables 1-3.
(5) Adhesion test A urethane-modified acrylic resin obtained in Examples and Comparative Examples was applied to a treated PET film at a film thickness of 10 μm and then dried at 50 ° C. for 30 minutes to prepare a test piece. Cross-cut the test piece into 2 mm wide squares, make 100 squares, apply cello tape (registered trademark) to these squares, and visually check for peeling of the coating when peeled off rapidly at an angle of 90 degrees Confirmed with. About 100 squares, the case where peeling was zero was set to “◯”, and the case where it was 1 or more was set to “x”. The results are shown in Tables 1-3.
It replaced with the said process PET film, and it operated similarly except using the polypropylene sheet which gave the corona treatment, and the presence or absence of peeling of a coating film was confirmed visually. About 100 squares, the case where peeling was zero was set to “◯”, and the case where it was 1 or more was set to “x”. The results are shown in Tables 1-3.
(6) Water resistance test A urethane-modified acrylic resin obtained in Examples and Comparative Examples was applied to a treated PET film with a film thickness of 10 μm, and then dried at 50 ° C. for 30 minutes to prepare a test piece. After immersing this test piece in 60 degreeC warm water for 4 hours, it pulled up and wiped off the surface water droplet, Then, the state (whitening, blistering) of the coating surface was observed visually. The results are shown in Tables 1-3.
(7) Adhesion test The urethane-modified acrylic resin obtained in Examples and Comparative Examples was applied to a treated PET film with a film thickness of 10 μm, and then dried at 50 ° C. for 30 minutes. Further, a UV curable resin was applied at a film thickness of 10 μm, dried at 50 ° C. for 30 minutes, and then photocured to prepare a test piece. Two types of UV curable resins, urethane acrylate (Hitaloid 7903-3, manufactured by Hitachi Chemical Co., Ltd.) and acrylic acrylate (Hitaloid 7975, manufactured by Hitachi Chemical Co., Ltd.) were used. Cross-cut the test piece into 2 mm wide squares, make 100 squares, apply cello tape (registered trademark) to these squares, and visually check for peeling of the coating when peeled off rapidly at an angle of 90 degrees Confirmed with. About 100 squares, the case where peeling was zero was set to “◯”, and the case where it was 1 or more was set to “x”.

  As a result of the test, the urethane-modified acrylic resins (I) to (IIIV) of Examples 1 to 8 were all good in weather resistance, adhesion, and water resistance. In Comparative Example 1 in which the hydroxyl value of the acrylic polyol was less than 5 mgHOH / g, peeling occurred in the weather resistance test and the adhesion test, and whitening was confirmed in the water resistance test. In Comparative Example 2 in which the hydroxyl value of the acrylic polyol exceeds 35 mgHOH / g and in Comparative Example 3 in which the weight average molecular weight exceeds 30000, the urethane-modified acrylic resin has gelled. In Comparative Example 4 where the acrylic polyol did not have an alicyclic skeleton, there was no abnormality in adhesion, but peeling occurred in the weather resistance test, and whitening was confirmed in the water resistance test. In Comparative Example 5 in which the polyol of component (B) did not have an alicyclic skeleton, there was no abnormality in the adhesion test, but peeling occurred in the weather resistance test, and whitening was confirmed in the water resistance test. In Comparative Example 6 where the acrylic / polyol ratio was not in the range of 30/70 to 70/30, evaluation was not possible because the acrylic / polyol ratio did not adhere to the base PET film.

Claims (4)

  An acrylic polyol (A) having an alicyclic skeleton, a hydroxyl value of 5 to 35 mg KOH / g, and a weight average molecular weight of 5000 to 30000, a polyol (B) having an alicyclic skeleton and other than an acrylic polyol, and an organic diisocyanate (C) is a urethane-modified acrylic resin obtained by urethanation reaction, and the mass ratio (A) / (B) of the polyol (B) to the acrylic polyol (A) is 30/70 to 70 /. 30 urethane-modified acrylic resin.   The urethane-modified acrylic resin according to claim 1, wherein the polyol (B) is a polyester polyol and / or a polycarbonate diol.   A coating agent comprising the urethane-modified acrylic resin according to claim 1.   An adhesive comprising the urethane-modified acrylic resin according to claim 1 or 2.