WO2009013576A1 - Diluants réactifs pour la modification de compositions de peinture thermodurcissables et compositions de peinture dans lesquelles ils sont utilisés. - Google Patents

Diluants réactifs pour la modification de compositions de peinture thermodurcissables et compositions de peinture dans lesquelles ils sont utilisés. Download PDF

Info

Publication number
WO2009013576A1
WO2009013576A1 PCT/IB2008/001710 IB2008001710W WO2009013576A1 WO 2009013576 A1 WO2009013576 A1 WO 2009013576A1 IB 2008001710 W IB2008001710 W IB 2008001710W WO 2009013576 A1 WO2009013576 A1 WO 2009013576A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydroxyl group
compound
group containing
reactive diluent
paint
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2008/001710
Other languages
English (en)
Inventor
Shinji Mitsumune
Yohei Koyama
Fusatada Nakamura
Shoichi Chida
Emi Leung
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Japan Ltd
Original Assignee
BASF Coatings Japan Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings Japan Ltd filed Critical BASF Coatings Japan Ltd
Publication of WO2009013576A1 publication Critical patent/WO2009013576A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/281—Monocarboxylic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds

Definitions

  • Reactive diluents for modifying thermosetting paint compositions and paint compositions in which they are used.
  • the invention concerns novel reactive diluents and paint compositions in which these reactive diluents are used for obtaining paint films which have excellent acid resistance and weather resistance and, in particular, excellent car-wash scratching resistance, in the automobile paint field for example.
  • Paint compositions which are characterized in that they contain from 10 to 50 wt% urethane polyol of weight average molecular weight from 1500 to 4000 and hydroxy1 group value from 50 to 180 mgKOH/g which have been obtained by reacting isocyanate compound and caprolactone polyol, from 30 to 80 wt% of fluorinated resin copolymer of hydroxyl group value from 50 to 150 mgKOH/g in which fluoro-olefin has been reacted as essential raw material and from 10 to 40 wt% of crosslinking agent are known as a method of rendering a paint film for automobile purpose unlikely to scratch in a car-wash (for example, see Patent Citation 1) .
  • the car-wash scratching resistance is inadequate and so the initial state is not maintained because of scratches which are produced when car-washing and, furthermore, there is a problem in that they are expensive since they contain fluorine.
  • paint compositions which are characterized in that they contain polyester oligomers of which the primary hydroxy1 group content is from 3 to 5 groups per molecule and the number average molecular weight is from 1501 to 3000 which are from 30 to 85% lactone modified and which have aliphatic hydrocarbyl groups which have from 4 to 22 carbon atoms originating from the lactone, and amino resin-based hardening agents which react with the hydroxy1 groups of the aforementioned hydroxyl group containing polyester oligomers, are known as paint compositions which have excellent gasoline resistance, scratching resistance, acid resistance and water resistance and which have in particular excellent chipping resistance
  • compositions comprising (A) hydroxyl group containing solvent soluble fluorine containing copolymer which has fluoro-olefin based polymer units and vinyl-based polymer units which have suspended polyester chains, (B) polycaprolactone polyol which has a number average molecular weight of from 200 to 3000, which has terminal hydroxyl groups and which has a hydroxyl group value of from 40 to 800 mgKOH/g and (C) hardening agent which has functional groups which react with hydroxyl groups are known as paint compositions which have excellent durability (scratching resistance) in respect of scratches caused by wiping with a duster or an automatic car-washing machine and chips caused by flying gravel and the like which is thrown up when driving (for example, see Patent Citation 3).
  • the car-wash scratching resistance is inadequate and so the initial state is not maintained due to scratches which are produced when car-washing and, furthermore, there is a problem in that they are expensive since they contain fluorine.
  • (A) which have a hydroxyl group value of from 200 to 400 mgKOH/g, and which include not more than 25 mass% of structural units based on lactone compounds in the resin solid fraction, hydroxyl group containing resins
  • crosslinking agent (C) which includes at least one or more functional group which reacts with hydroxyl groups in the molecules which are characterized in that the proportions of the hydroxyl group containing resin (A) and the hydroxyl group containing resin (B) , as the mass ratio of the resin solid fractions, are (A) / (B) from 90/10 to 10/90 are known as paint compositions with which paint films which have excellent car-wash scratching resistance, acid resistance, staining resistance, water resistance and weather resistance can be obtained (for example, see Patent Citation 4) .
  • these hydroxyl group containing resins (A) and (B) are both acrylic resins which have a weight average molecular weight of from 1,000 to 30,000 and the flexibility is inadequate and so there is a problem in that the car-wash scratching resistance is inadequate.
  • the invention provides a reactive diluent comprising a hydroxyl group containing resin which has been obtained by reacting at the same time (a) a compound where two or more hydroxyl groups are included in one molecule, (b) a compound where two non- sulfur modified isocyanate groups are included in one molecule and (c) a lactone compound which is characterized in that said hydroxyl group containing resin has a hydroxyl group value of from 100 to 200 mgKOH/g and a weight average molecular weight of from 1,000 to 2,000, and contains from 20 to 40 mass% of structural units based on the lactone compound of the (c) component.
  • the invention provides a reactive diluent comprising a hydroxyl group containing resin which has been obtained by reacting (a) a compound where two or more hydroxyl groups are included in one molecule and (b) a compound where two non-sulfur modified isocyanate groups are included in one molecule and then carrying out an addition reaction of (c) a lactone compound, characterized in that said hydroxyl group containing resin has a hydroxyl group value of from 100 to 200 mgKOH/g and a weight average molecular weight of from 1,000 to 2,000, and contains from 20 to 40 mass% of structural units based on the lactone compound of the (c) component. [0011]
  • thermosetting paint composition characterized in that it includes the abovementioned reactive diluent, hydroxyl group containing acrylic resin which has a hydroxyl group value of from 80 to 150 mgKOH/g and a weight average molecular weight of from 3,000 to 100,000 and polyfunctional isocyanate compound and in which the proportion of the contents of said reactive diluent and said hydroxyl group containing acrylic resin as the resin mass ratio is within the range from 5/95 to 15/85.
  • the invention provides a thermosetting paint composition in which, in the abovementioned thermo-setting paint composition, the polyfunctional isocyanate compound is an isocyanurate compound.
  • thermosetting paint composition On using a reactive diluent of this invention in a thermosetting paint composition it functions as a diluent and reacts with the hardening agent and forms a hardened resin component, and paint films which have excellent acid resistance and weather resistance can be formed, and in particular paint films which have excellent car-wash scratching resistance can be formed and, furthermore, the painting operability is excellent. Furthermore, the compatibility with the hydroxyl group containing resins which are used as the resin components of thermo-setting paint compositions is excellent.
  • a reactive diluent of this invention is obtained by reacting (a) compound which includes two or more hydroxyl groups, (b) compound which includes two non- sulfur modified isocyanate groups and (c) lactone compound, and the (a) component, the (b) component and the (c) component may be reacted at the same time or the (a) component and the (b) component may be reacted first and then an addition reaction can be carried out with the (c) component.
  • the (a) component which is used in the invention is a compound where two or more hydroxyl groups are included in one molecule, and the polyhydric alcohols which are generally used as polyester raw materials can be cited as ideal practical examples.
  • radically polymerizable monomers and acrylic resin oligomers which have been obtained by polymerizing radically polymerizable monomers are undesirable for the (a) component of this invention in that flexibility is difficult to achieve.
  • Examples of actual polyhydric alcohols of the (a) component include the following dihydric and trihydric and higher alcohols.
  • the dihydric alcohols include glycols such as ethylene glycol propylene glycol, diethylene glycol, triethylene glycol, 1,4- butanediol, 1, 3-butanediol, 2 , 3-butanediol, 1,2- butanediol, 1, 5-pentanediol, 1, 4-pentanediol, 2, 4-pentanediol, 2 , 3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4, 5-pentanediol, 2,2, 4-trimethyl-l, 3-pentanediol, 1, 6-hexanediol, 1, 5-hexanediol, 1, 4-hexanediol, 2 , 5-hexanediol, 1, 4-cyclohexanedimethanol, ne
  • glycerine, trimethylolethane, trimethylolpropane, diglycerine, pentaerythritol, dipentaerythritol, sorbitol and the like can be cited as examples of trihydric and higher alcohols and, furthermore, compounds which have two or more epoxy groups in the molecule such as bisphenol A diglycidyl ether can also be used as trihydric or higher alcohols.
  • trimethylolpropane, dimethylolpropionic acid, dimethylolbutanoic acid, hydrogenated bisphenol A and 1, 4-cyclohexanedimethanol are preferred from the viewpoint of the balance between the flexibility and hardness of the paint compositions in which the reactive diluent is used, and combinations of trimethylolpropane (TMP) and 1, 4-cyclohexanedimethanol (CHDM) in which the TMP and CHDM mol ratio is within the range from 15/85 to 45/55 are more desirable, and those combinations where the mol ratio is within the range from 20/80 to 40/60 are especially desirable, from the viewpoint of the balance of hardness and flexibility.
  • TMP trimethylolpropane
  • CHDM 4-cyclohexanedimethanol
  • dimethylolalkanoic acids such as dimethylolpropionic acid and dimethylolbutanoic acid which have carboxyl groups among the polyhydric alcohols likewise also fulfill the role as acid catalysts for esterification reactions and urethanization reactions, but an acid catalyst may be used in those cases where a dimethylolalkanoic acid is not used.
  • the (b) component used in the invention is a compound which includes two non-sulfur modified isocyanate groups in one molecule.
  • Aliphatic di-functional isocyanates such as hexamethylene diisocyanate (HDI) and alicyclic difunctional diisocyanates such as isophorone diisocyanate (IPDI), 4, 4 ' -diphenylmethanediisocyanate (MDI) and 4, 4 'methylenebis (cyclohexylisocyanate) (hydrogenated MDI) can be used as actual examples of the (b) component, but isophorone diisocyanate is especially desirable from the viewpoint of the balance of flexibility and hardness of a paint composition in which the reactive diluent is used.
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • MDI 4, 4 ' -diphenylmethanediisocyanate
  • MDI 4, 4 'methylenebis (cyclohexylisocyanate) (hydrogenated MDI)
  • One type of (b) component may be used alone, or a combination of two or more types can be used.
  • ⁇ -Caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -nonanoiclactone, ⁇ -dodecanolactone and the like can be cited as actual examples of the lactone compounds which can be used for the (c) component of this invention, but ⁇ -caprolactone in particular is preferred.
  • One type of lactone may be used for the (c) component, or a combination of two or more types may be used.
  • the hydroxyl group value of a hydroxyl group containing resin which is a reactive diluent of this invention is preferably from 100 to 200 mgKOH/g, more desirably from 130 to 190 mgKOH/g, and most desirable from 150 to 190 mgKOH/g.
  • a hydroxyl group value of the hydroxyl group containing resin which is a reactive diluent of less than 100 mgKOH/g paint film hardness is not obtained and the staining resistance is reduced, and in those cases where it exceeds 200 mgKOH/g the SP (solubility parameter) value of the resin rises and differs from the SP value of the hardening agent and the compatibility is reduced and so appearance-failure of the paint film occurs.
  • the weight average molecular weight of a hydroxyl group containing resin which is a reactive diluent of this invention is preferably from 1,000 to 2,000, more desirably from 1,400 to 2,000, and most desirably from 1,600 to 1,800.
  • a weight average molecular weight of the hydroxyl group containing resin which is a reactive diluent of this invention of less than 1,000 it is difficult to obtain satisfactory film hardness, and in those cases where it exceeds 2,000 appearance- failure of the paint film arises due to the reduced compatibility with hydroxyl group containing acrylic resins.
  • the proportion of the (c) component included in a hydroxyl group containing resin which is a reactive diluent of this invention as structural units based on a lactone compound in the hydroxyl group containing resin which is a reactive diluent is preferably from 20 to 40 mass%, more desirably from 25 to 40 mass%, and most desirably from 30 to 40 mass%.
  • a proportion of (c) component of the hydroxyl group containing resin which is a reactive diluent of less than 20 mass% the car-wash scratching resistance of the paint film is reduced, and in those cases where it exceeds 40 mass% the compatibility of the paint is reduced and the hardness and staining resistance of the paint film are reduced.
  • the reaction for obtaining a hydroxyl group containing resin which is a reactive diluent comprises two reactions, namely an addition reaction I of a compound which includes two or more hydroxyl groups which is the (a) component and a compound which includes two non-sulfur modified isocyanate groups which is the (b) component, and the addition reaction II of a lactone compound which is the (c) component on the hydroxyl groups of the compound which includes two or more hydroxyl groups which is the (a) component or the compound obtained in addition process I.
  • the addition reaction I involves reaction for from 1 to 3 hours under temperature conditions from 110 to 130 0 C and addition reaction II involves reaction for from 2 to 4 hours under temperature conditions from 140 to 160 0 C.
  • a reaction catalyst which can be used in urethane paints generally can be used in the reaction of the isocyanate compound and the hydroxy1 group containing compound in addition reaction I.
  • tin-based catalysts such as dibutyltin dilaurylate, acid-based catalysts such as organic carboxylic acids and basic catalysts such as tertiary amines can be cited as actual reaction catalysts.
  • the reactive diluent can be synthesized in a solvent, but preferably alcohol-based solvents are not used so that there is no reaction with the isocyanate groups.
  • Aromatic solvents, ester-based solvents, ketone-based solvents and the like can be cited as preferred solvents.
  • the reactive diluent may include solvent but a smaller the solvent content is desirable.
  • the preferred solvent content is preferably not more than 50 mass%, and more desirably not more than 45 mass%, with respect to the total amount of reactive diluent.
  • a reactive diluent of this invention can be used for a thermosetting paint composition in which it is used with a poly-functional isocyanate compound which is a crosslinking agent which reacts with the hydroxyl groups of the hydroxyl group containing resin which is the reactive diluent and the hydroxyl groups of a hydroxyl group containing acrylic resin.
  • a reactive diluent of this invention fulfils the role of the modifying agent of a hydroxyl group containing acrylic resin and the mixing proportions of reactive diluent and hydroxyl group containing acrylic resin as the resin mass ratio is preferably in the range from 5/95 to 15/85, and more desirably in the range from 7/93 to 13/87.
  • the hydroxyl group containing acrylic resin can be obtained by copolymerizing a hydroxyl group containing acrylic monomer with other radically polymerizable monomer in accordance with the usual acrylic resin synthesizing conditions.
  • the weight average molecular weight of the hydroxyl group containing acrylic resin is preferably from 3,000 to 100,000, more desirably from 3,000 to 50,000, and most desirably from 4,000 to 30,000.
  • a hydroxyl group containing acrylic resin of weight average molecular weight less than 3,000 the hardenability is poor, and in those cases where it exceeds 100,000 the viscosity when forming a paint film is high and so the paint film appearance declines.
  • the hydroxyl group value of the hydroxyl group containing acrylic resin is preferably from 80 to 150 mgKOH/g, and more desirably from 90 to 145 mgKOH/g.
  • 2-Hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth) acrylate, allyl alcohol, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and the ethylene oxide and/or propylene oxide adducts of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and the like can be cited as hydroxyl group containing acrylic resin hydroxyl group containing monomers , but from the viewpoints of hardness and flexibility 4-hydroxybutyl (meth) acrylate is especially desirable.
  • a radical polymerization initiator may be compounded when carrying out the radical copolymerization of the abovementioned radically polymerizable monomers.
  • radical polymerization initiators include azo compounds such as 2,2' -azobisisobutyronitrile, 2,2' -azobis-2 , 4-dimethyl- valeronitrile, 4, 4 ' -azobis-4-cyanovaleric acid, 1-azo- bis-1-cyclohexanecarbonitrile, dimethyl-2 , 2 ' -azobis- isobutyrate and the like, and organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3 , 5, 5-trimethylhexanone peroxide, 1, 1-bis (t-butyl- peroxy) -3,3, 5-trimethylcyclohexane, 1, 1-bis (t-butyl- peroxy) cyclohexane, 2 , 2-bis (t-butylperoxy) o
  • radical polymerization initiator compounded No particular limitation is imposed upon the amount of radical polymerization initiator compounded, but an amount of from 0.01 to 20 mass% with respect to the total amount of radically polymerizable monomer is preferred.
  • Reducing agents such as dimethylaniline, ferrous salts such as ferrous sulfate, ferrous chloride, ferrous acetate and the like, acidic sodium sulfite, sodium thiosulfate, rongalite and the like may, of course, be included, as required, in these radical polymerization initiator systems, but they must be selected with care so that the polymerization temperature is as low as possible.
  • Poly-functional isocyanate compounds are preferred for the hardening agents which are used in the abovementioned thermosetting paint compositions, and p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate, 3 , 3 ' -dimethyl-4 , 4 ' -biphenylene diisocyanate, 1, 4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2 , 2 , 4-trimethylhexane-l, 6- diisocyanate, methylenebis (phenylisocyanate) , lysine methyl ester diisocyanate, bis (isocyanatoethyl) fumarate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanatoethyl-2 , 6-diisocyanato- hexanoate and the biuret forms (three isocyanate groups per molecule
  • the isocyanate compound may or may not be blocked, and isocyanate compounds where polyisocyanate compounds which have two or more isocyanate groups in one molecule, for example polyisocyanates such as hexamethylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate and the like, have been blocked with an active methylene based blocking agent such as methyl acetoacetate, dimethyl malonate and the like, or an oxime-based blocking agent can be cited as examples of isocyanate compounds which have blocked isocyanate groups.
  • polyisocyanates such as hexamethylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate and the like
  • an active methylene based blocking agent such as methyl acetoacetate, dimethyl malonate and the like
  • an oxime-based blocking agent can be cited as
  • the preferred proportions in which the hydroxyl group containing resin which is the reactive diluent used in this invention, the hydroxyl group containing acrylic resin and the polyfunctional isocyanate compound are included are such that the amount of isocyanate group compounded with respect to the hydroxyl groups in the reactive diluent and hydroxyl group containing acrylic resin as the functional group ratio is preferably from 1/0.5 to 1/1.5, and more desirably from 1/0.8 to 1/1.2.
  • thermosetting paint compositions of this invention can be used as they are, or they can be used with the addition of organic solvents and various additives, for example one or more of ultraviolet absorber, photo-stabilizer, antioxidant, surfactant, surface controlling agent, hardening reaction catalyst, anti-static agent, perfume, de-watering agent and rheology controlling agents such as polyethylene wax, polyamide wax, fine internally crosslinked type resin particles and the like, as required.
  • additives for example one or more of ultraviolet absorber, photo-stabilizer, antioxidant, surfactant, surface controlling agent, hardening reaction catalyst, anti-static agent, perfume, de-watering agent and rheology controlling agents such as polyethylene wax, polyamide wax, fine internally crosslinked type resin particles and the like, as required.
  • thermosetting paint compositions of this invention may be used as clear paints, or coloring agents such as dyes and pigments may be compounded and they may be used as colored paints .
  • thermosetting paint compositions of this invention are preferably used as top-coat paint compositions.
  • the finish-painting method of a top-coat paint of this invention may be, for example, a two-coat one-bake finish-painting method where a colored base- coat is painted on a base material and in the un- crosslinked state a thermosetting paint composition of this invention is applied as a top-coat paint, the overcoat finish-painting method where a colored based coat is painted on a base material and, in the un- hardened state, a top-coat paint is applied and they are baked at the same time, and then a paint composition of this invention is applied as an overcoat paint and baked, and the finish-painting method in which, in the aforementioned over-coat finish-painting method, a primer paint is applied in order to ensure adhesion of the base-coat and, in the un-crosslinked state, a thermosetting paint composition of this invention is applied as an over-coat paint.
  • the aforementioned colored base coat paints, topcoat paints, over-coat paints and primer paints are adjusted to the prescribed viscosity, sometimes by heating or by adding organic solvents and reactive diluents, as required, and then painting is carried out using a painting machine as generally used such as a painting machine of the air sprayer, electrostatic air sprayer, roll coater, flow coater or dipping type, or using a brush or a bar coater, applicator or the like. From among these spray painting is preferred.
  • thermosetting paint compositions of this invention include both organic materials and inorganic materials such as wood, glass, metal, cloth, plastics, foams, elastomers, paper, ceramics, concrete, plaster-board and the like. These base materials may be in an un-surface-treated state, or a paint film may have been formed on the surface beforehand.
  • thermosetting paint composition of this invention is not limited by the practical examples.
  • a film thickness after drying of from 10 to 150 ⁇ m is preferred, and a film thickness after drying of from 10 to lOO ⁇ m is especially desirable.
  • coated objects which can be obtained with the method of coating of this invention include structural materials, wooden products, metal products, plastic products, rubber products, worked paper, ceramic products, glass products and the like.
  • these include automobiles and automobile parts (for example bodies, bumpers, spoilers, mirrors, wheels, interior decorative parts and the like, which are made of a variety of materials), metal sheets such as steel sheets, bicycles, bicycle parts, materials used on roads (for example guard rails, traffic signs, sound-deadening walls and the like) , materials used in tunnels (for example side wall panels and the like), ships, railway rolling stock, aircraft, furniture, musical instruments, domestic electrical goods, building materials, containers, office accessories, sports accessories, toys and the like.
  • automobiles and automobile parts for example bodies, bumpers, spoilers, mirrors, wheels, interior decorative parts and the like, which are made of a variety of materials
  • metal sheets such as steel sheets, bicycles, bicycle parts, materials used on roads (for example guard rails, traffic signs, sound-deadening walls and the like)
  • materials used in tunnels for example side wall panels and the like
  • ships railway rolling stock, aircraft, furniture, musical instruments, domestic electrical goods, building materials, containers, office accessories, sports accessories, toys and the like
  • the invention is described in more practical terms below by means of examples and comparative examples . Moreover, where there is no indication to the contrary "parts” and “%” signify “parts by mass” and “mass%” respectively. Moreover, the resin solid fraction is the residue on heating measured with the method described in JIS K5601-1-2. [0034]
  • the reactive diluents D-3 to D-9 were synthesized in the same way as reactive diluent D-I except that the raw materials were changed as shown in Table 1 and Table 2.
  • a drip-feed component where radically polymerizable monomer comprising 9 parts of styrene, 21.6 parts of 4- hydroxybutyl acrylate, 15.2 parts of n-butyl acrylate, 13.8 parts of n-butyl methacrylate and 0.4 part of acrylic acid and 0.8 part of t-butylperoxy-2- ethylhexanoate as polymerization initiator had been mixed together uniformly was drip-fed from the dropping funnel at an even rate over a period of 2 hours at a temperature of 140 0 C. After the drip-feed had been completed the temperature was maintained at 140 0 C for 1 hour and then the reaction temperature was lowered to 115°C.
  • the clear paints CC-I to CC-13 were prepared by mixing together successively the raw materials shown in Table 4 and Table 5 and stirring to provide uniform mixtures .
  • Crosslinking Agent N3300 Desmodur N3300, Trade name, a liquid HDI isocyanurate type resin (involatile fraction 100 mass%, NCO content 23 mass%) , produced by the Sumika Bayer Urethane Co .
  • Ultraviolet absorber solution A 20 mass% xylene solution of Tinuvin 900, trade name, produced by the Ciba Specialty Chemical Co.
  • Photo-stabilizer solution A 20 mass% xylene solution of Tinuvin 292, trade name, produced by the Ciba Specialty Chemical Co.
  • the paint film hardness was measured at 25°C using a Kernich oscillating probe hardness meter produced by the Ericssen Co., and evaluation was carried out.
  • the Kernich oscillating probe hardness meter measures the paint film hardness by establishing the tip of the vibrating probe on the paint film which has been arranged in the horizontal orientation and a higher hardness is indicated by a larger number of oscillations .
  • the 60° mirror surface gloss of the paint film was measured with a digital variable-angle gloss meter
  • ⁇ Gloss retention rate at least 80% but less than 90%
  • X Gloss retention rate less than 80%
  • a 40% sulfuric acid aqueous solution (0.2 ml) was located as a spot on a test sheet and heated to 60 0 C for 15 minutes and then rinsed off with water and the extent of formation of a staining mark was observed visually.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention vise à proposer des compositions de peinture avec lesquelles des films de peinture qui présentent d'excellentes propriétés de résistance aux acides, de résistance à l'eau et de résistance aux intempéries, et, en particulier une excellente résistance à la rayure par des portiques de lavage des voitures, peuvent être formés, ainsi que des diluants réactifs qui peuvent être utilisés pour obtenir ces compositions de peinture. A cet effet, l'invention porte sur un diluant réactif comprenant une résine à teneur en groupe hydroxyle qui a été obtenue par réaction (a) d'un composé où deux groupes hydroxyle ou davantage sont compris dans une molécule, (b) un composé où deux groupes isocyanate non modifiés par du soufre sont inclus dans une molécule et (c) un composé lactone, caractérisé par le fait que ladite résine à teneur en groupe hydroxyle a un indice de groupe hydroxyle de 100 à 200 ngKOH/g et une masse moléculaire moyenne en poids de 1 000 à 2 000, et contient de 20 à 40% en masse d'unités structurales à base du composé lactone du composant (c), et sur des compositions de peinture thermodurcissables qui contiennent ces diluants réactifs et des résines acryliques à teneur en groupe hydroxyle.
PCT/IB2008/001710 2007-07-24 2008-06-25 Diluants réactifs pour la modification de compositions de peinture thermodurcissables et compositions de peinture dans lesquelles ils sont utilisés. Ceased WO2009013576A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007-192675 2007-07-24
JP2007192675A JP4539688B2 (ja) 2007-07-24 2007-07-24 熱硬化性塗料組成物を改質する反応性希釈剤及びそれを用いた塗料組成物

Publications (1)

Publication Number Publication Date
WO2009013576A1 true WO2009013576A1 (fr) 2009-01-29

Family

ID=39790266

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2008/001710 Ceased WO2009013576A1 (fr) 2007-07-24 2008-06-25 Diluants réactifs pour la modification de compositions de peinture thermodurcissables et compositions de peinture dans lesquelles ils sont utilisés.

Country Status (2)

Country Link
JP (1) JP4539688B2 (fr)
WO (1) WO2009013576A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103013256A (zh) * 2012-12-24 2013-04-03 青岛宣威涂层材料有限公司 一种隐身涂层材料及其制备方法
CN112384549A (zh) * 2020-08-13 2021-02-19 擎天材料科技有限公司 一种端羟基聚酯树脂及其制备方法和应用
CN116731668A (zh) * 2023-08-11 2023-09-12 拓迪化学(上海)有限公司 粘附性底涂剂组合物及粘附性底涂剂制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102039470B1 (ko) * 2017-12-12 2019-11-04 주식회사 노루비케미칼 내스크래치성 고경도 도막을 형성하기 위한 자동차 외장용 코팅 조성물 및 이를 이용한 자동차 외장의 코팅 방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2193504A (en) * 1986-07-24 1988-02-10 Basf Corp Utilization of lactones and lactams in the preparation of polyurethane-polyurea microcellular foams
DE19723895A1 (de) * 1997-06-06 1998-12-10 Yoon Jick Dipl Ing Lee Bioabbaubare Polyesterurethane, Verfahren zu ihrer Herstellung sowie ihre Verwendung
DE19928687A1 (de) * 1999-06-23 2000-12-28 Basf Ag Polyisocyanat-Polyadditionsprodukte
WO2003004544A1 (fr) * 2001-07-05 2003-01-16 Rhodia Chimie Composition polycondensable comportant un heterocycle oxygene et un isocyanate, et procede de polycondensation y afferant
EP1479704A2 (fr) * 2003-05-20 2004-11-24 Bayer MaterialScience AG Combinaisons de liants aqueux ayant une haute teneur en solides pour des laques de finition résistantes aux rayures

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01156375A (ja) * 1987-11-19 1989-06-19 E I Du Pont De Nemours & Co 有機溶剤ベース熱硬化性コーティング組成物
JP2693999B2 (ja) * 1989-02-22 1997-12-24 関西ペイント株式会社 塗装仕上げ方法
JPH0551556A (ja) * 1991-08-27 1993-03-02 Nippon Oil & Fats Co Ltd 塗料組成物
JP2000007985A (ja) * 1998-06-23 2000-01-11 Sumitomo Rubber Ind Ltd ポリウレタン塗料
JP4073111B2 (ja) * 1999-03-26 2008-04-09 株式会社イノアックコーポレーション 難黄変ポリウレタンフォーム及びその製造方法
JP2003292928A (ja) * 2002-02-04 2003-10-15 Toyo Ink Mfg Co Ltd ウレタン樹脂粘着剤及び積層体
JP4872247B2 (ja) * 2005-06-16 2012-02-08 Ｂａｓｆコーティングスジャパン株式会社 熱硬化性塗料組成物
JP4894190B2 (ja) * 2005-08-04 2012-03-14 Ｂａｓｆコーティングスジャパン株式会社 塗料組成物、塗装仕上げ方法及び塗装物品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2193504A (en) * 1986-07-24 1988-02-10 Basf Corp Utilization of lactones and lactams in the preparation of polyurethane-polyurea microcellular foams
DE19723895A1 (de) * 1997-06-06 1998-12-10 Yoon Jick Dipl Ing Lee Bioabbaubare Polyesterurethane, Verfahren zu ihrer Herstellung sowie ihre Verwendung
DE19928687A1 (de) * 1999-06-23 2000-12-28 Basf Ag Polyisocyanat-Polyadditionsprodukte
WO2003004544A1 (fr) * 2001-07-05 2003-01-16 Rhodia Chimie Composition polycondensable comportant un heterocycle oxygene et un isocyanate, et procede de polycondensation y afferant
EP1479704A2 (fr) * 2003-05-20 2004-11-24 Bayer MaterialScience AG Combinaisons de liants aqueux ayant une haute teneur en solides pour des laques de finition résistantes aux rayures

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103013256A (zh) * 2012-12-24 2013-04-03 青岛宣威涂层材料有限公司 一种隐身涂层材料及其制备方法
CN112384549A (zh) * 2020-08-13 2021-02-19 擎天材料科技有限公司 一种端羟基聚酯树脂及其制备方法和应用
CN112384549B (zh) * 2020-08-13 2023-03-28 擎天材料科技有限公司 一种端羟基聚酯树脂及其制备方法和应用
CN116731668A (zh) * 2023-08-11 2023-09-12 拓迪化学(上海)有限公司 粘附性底涂剂组合物及粘附性底涂剂制备方法
CN116731668B (zh) * 2023-08-11 2023-11-10 拓迪化学(上海)股份有限公司 粘附性底涂剂组合物及粘附性底涂剂制备方法

Also Published As

Publication number Publication date
JP4539688B2 (ja) 2010-09-08
JP2009029856A (ja) 2009-02-12

Similar Documents

Publication Publication Date Title
US8236895B2 (en) Paint compositions, a method of finish-painting and painted objects
JP6466977B2 (ja) 複層塗膜形成方法
KR101531569B1 (ko) 수성 도료 조성물 및 이를 사용한 도막의 형성방법
KR20090049073A (ko) 코팅용 수지 조성물 및 이를 이용한 코팅 조성물
JP4539688B2 (ja) 熱硬化性塗料組成物を改質する反応性希釈剤及びそれを用いた塗料組成物
US8143341B2 (en) Aqueous coating compositions
EP1907493B1 (fr) Compositions de peinture et objets peints
JP2020196870A (ja) 水系２成分型硬化樹脂組成物及び物品のコーティング方法
US7906580B2 (en) Paint composition, a method of paint finishing and painted objects
JP7724092B2 (ja) 土木建築用コーティング樹脂組成物、硬化膜、土木建築構造物のコーティング方法、タイルの剥落防止方法、及び構造体
CN110773402A (zh) 多层涂层及其形成方法
JP7532375B2 (ja) 水性コーティングの低温硬化
US8349972B2 (en) Paint compositions, a method of paint finishing and painted objects
EP3399002B1 (fr) Composition de peinture du type à un composant, hautement résistante aux rayures
JP7353542B1 (ja) 水性多液型ポリウレタン塗料組成物
JP4595639B2 (ja) 塗料組成物、塗装仕上げ方法及び塗装物品
EP1798266A2 (fr) Composition de resine a groupes hydroxyle pour revetements, composition de revetement, procede de revetement de finition et article revetu
KR20040073184A (ko) 자동차의 복층 도막 형성방법
Heischkel et al. Influence of crosslinking density of radiation curable coatings on scratch resistance, hardness and flexibility
KR20250090099A (ko) 고광택 클리어 도료 조성물
TR2024007646T2 (tr) Bloke poli?i?zosi?yanat ve aynisini i?çeren suda çözünür şeffaf kaplama bi?leşi?mi?

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08762982

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08762982

Country of ref document: EP

Kind code of ref document: A1