WO2018135418A1 - ポリオレフィン系塗料組成物 - Google Patents
ポリオレフィン系塗料組成物 Download PDFInfo
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- WO2018135418A1 WO2018135418A1 PCT/JP2018/000758 JP2018000758W WO2018135418A1 WO 2018135418 A1 WO2018135418 A1 WO 2018135418A1 JP 2018000758 W JP2018000758 W JP 2018000758W WO 2018135418 A1 WO2018135418 A1 WO 2018135418A1
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- modified polyolefin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
- C09D123/30—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by oxidation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
- C08L45/02—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers of coumarone-indene polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers
- C09D145/02—Coumarone-indene polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Definitions
- the present invention is characterized by containing an acid-modified polyolefin and a coumarone-indene resin, and relates to a coating composition having good coating storage stability, adhesion to a polyolefin substrate, and good chemical resistance.
- Patent Document 1 discloses a primer coating composition using an acid-modified chlorinated polyolefin and a dispersion resin.
- Patent Document 2 discloses an aqueous coating composition using acid-modified polyolefin and coumarone resin or indene resin.
- Patent Document 1 uses acid-modified chlorinated polyolefin as a resin component for the primer, which has environmental problems and cannot be said to have sufficient chemical resistance. It was. Further, Patent Document 2 describes an aqueous dispersion, which cannot be said to have sufficient water resistance and chemical resistance.
- the object of the present invention is to be used as a primer for a polypropylene base material used for automobile bumpers and the like, and has excellent adhesion and chemical resistance such as water resistance, gasohol resistance and fuel resistance compared to conventional bumper primers. And a coating composition having good storage stability of the coating.
- the present inventors have blended a specific coumarone-indene resin and a specific solvent together with an acid-modified polyolefin, so that the adhesiveness and chemical resistance are excellent and the storage stability of the paint is excellent.
- the present invention was reached by finding that a suitable coating film was obtained.
- the present invention has the following configuration.
- Including acid-modified polyolefin (A), coumarone-indene resin (B) and hydrocarbon solvent (C), Coumarone-indene resin (B) is 25 to 400 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (A), Furthermore, the coating composition characterized by including at least one of an ester solvent or a ketone solvent (D).
- the acid value of the acid-modified polyolefin (A) is preferably 5 to 40 mg KOH / g-resin, and the weight average molecular weight is preferably 20,000 to 180,000.
- the hydrocarbon-based solvent (C) is preferably contained in an amount of 200 to 3000 parts by mass and more preferably an alcohol-based solvent (E) with respect to 100 parts by mass of the acid-modified polyolefin (A).
- Primer paint for polyolefin substrates containing the paint composition are listed below.
- the present invention it is possible to form a coating film excellent in chemical resistance such as water resistance, gasohol resistance and fuel resistance and adhesion, and a coating composition having good storage stability can be obtained.
- the coating composition of the present invention comprises an acid-modified polyolefin (A), a coumarone / indene resin (B), a hydrocarbon solvent (C), and a multi-component comprising a combination of an ester solvent or a ketone solvent (D).
- A acid-modified polyolefin
- B coumarone / indene resin
- C hydrocarbon solvent
- D multi-component comprising a combination of an ester solvent or a ketone solvent
- the composition of the system is also useful as a primer for a polyolefin substrate.
- a polypropylene substrate is particularly preferable.
- the coating composition of the present invention contains an acid-modified polyolefin (A) and a coumarone / indene resin (B), and the coumarone / indene resin (B) is contained in an amount of 25 to 400 per 100 parts by mass of the acid-modified polyolefin (A). Including parts by mass.
- the coumarone-indene resin (B) is preferably 30 parts by mass or more, more preferably 60 parts by mass or more, and still more preferably 100 parts by mass or more with respect to 100 parts by mass of the acid-modified polyolefin (A). . If the amount is too small, the storage stability of the paint may be lowered. Moreover, it is preferable that it is 350 mass parts or less, More preferably, it is 300 mass parts or less, More preferably, it is 200 mass parts or less. If the amount is too large, adhesion and chemical resistance may decrease.
- the acid-modified polyolefin (A) at least one of ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydride thereof is grafted onto at least one of polyethylene, polypropylene, and propylene- ⁇ -olefin copolymer. What is obtained by this is preferable.
- the propylene- ⁇ -olefin copolymer is a copolymer in which ⁇ -olefin is copolymerized mainly with propylene.
- ⁇ -olefin for example, one kind or several kinds of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like can be used. Of these ⁇ -olefins, ethylene and 1-butene are preferred.
- the ratio of the propylene component to the ⁇ -olefin component of the propylene- ⁇ -olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.
- the coating composition of the present invention has good adhesion, chemical resistance and coating storage stability. Furthermore, even if the ethylene component content is 30 mol% or less, the coating composition of the present invention exhibits sufficient adhesion, chemical resistance and coating storage stability, and the ethylene component content is 9 mol% or less. It doesn't matter.
- Examples of at least one of ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydrides thereof include maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof.
- acid anhydrides are preferable, and maleic anhydride is more preferable.
- Specific examples include acid-modified polypropylene, acid-modified propylene-ethylene copolymer, acid-modified propylene-butene copolymer, acid-modified propylene-ethylene-butene copolymer, and the like. Two or more types can be used in combination.
- the weight average molecular weight (Mw) of the acid-modified polyolefin (A) is preferably in the range of 20,000 to 180,000. More preferably, it is in the range of 40,000 to 180,000. If it is less than the above value, chemical resistance may be inferior. On the other hand, when the above value is exceeded, a problem may occur in the paint storage stability.
- the acid value of the acid-modified polyolefin (A) is preferably in the range of 5 to 40 mg KOH / g-resin from the viewpoint of adhesion to the polyolefin resin substrate. More preferably, it is in the range of 10 to 30 mg KOH / g-resin. If it is less than the above value, a problem may occur in the storage stability of the paint. On the other hand, when the above value is exceeded, chemical resistance may be inferior.
- the acid-modified polyolefin (A) melting point (Tm) is preferably 40 ° C or higher, more preferably 50 ° C or higher. If it is too low, adhesion and chemical resistance may be lowered. Moreover, it is preferable that it is 120 degrees C or less, More preferably, it is 100 degrees C or less. If it is too high, the coating storage stability may be lowered.
- the heat of fusion ( ⁇ H) of the acid-modified polyolefin (A) is preferably 5 J / g or more, more preferably 10 J / g or more. If it is too small, the adhesion and chemical resistance may decrease. Moreover, it is preferable that it is 60 J / g or less, More preferably, it is 50 J / g or less. If it is too high, the coating storage stability may be lowered.
- the acid-modified polyolefin (A) is preferably substantially not chlorinated. If it is substantially chlorinated, it is not only an environmental problem, but chemical resistance may be reduced. “Not substantially chlorinated” means that the chlorine content is preferably 10 wt% or less, more preferably 5 wt% or less, still more preferably 1 wt% or less, and particularly preferably 0 wt%. .
- the acid-modified polyolefin (A) is preferably crystalline. Being crystalline, it has excellent adhesion and chemical resistance compared to amorphous.
- crystalline means that the temperature is raised from ⁇ 100 ° C. to 250 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC) and shows a clear melting peak in the temperature raising process.
- DSC differential scanning calorimeter
- the method for producing the acid-modified polyolefin (A) is not particularly limited, and for example, radical graft reaction (that is, generating radical species for the polymer to be the main chain, and using the radical species as a polymerization initiation point, the unsaturated carboxylic acid and Reaction for graft polymerization of an acid anhydride), and the like.
- radical graft reaction that is, generating radical species for the polymer to be the main chain, and using the radical species as a polymerization initiation point, the unsaturated carboxylic acid and Reaction for graft polymerization of an acid anhydride
- organic peroxide is not particularly limited, but di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy- Peroxides such as 2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide; azobisisobutyronitrile, azobisisopropionitrile, etc. Examples thereof include azonitriles.
- the coumarone-indene resin (B) is mainly composed of coumarones and indenes as monomer components.
- coumarones and indenes are contained in the coumarone-indene resin in a total amount of 50% by mass or more, and more preferably 60% by mass or more.
- Specific examples of coumarones include coumarone and methylcoumarone, and specific examples of indenes include inden and methylindene.
- monomer components other than coumarones and indenes include styrene, vinyl toluene, and dicyclopentadiene.
- the monomer composition is appropriately selected depending on the use of the resin and the like, but is usually about 1 to 80% by mass for coumarones and about 20 to 95% by mass for indenes.
- Styrene is preferably contained in an amount of 1 to 20% by mass.
- the coumarone-indene resin may contain a hydroxyl group or a carboxylic acid group.
- the softening point of the coumarone-indene resin (B) is not particularly limited, but it is 60 ° C. from the viewpoint of applicability to desired applications, good blending properties, coating properties, and adhesion.
- the temperature is preferably above, and more preferably 70 to 170 ° C.
- the weight average molecular weight (Mw) of the coumarone-indene resin (B) is preferably in the range of 100 to 2000, more preferably in the range of 500 to 1500. If it is less than the above value, the adhesion of the paint may be inferior. On the other hand, if the above value is exceeded, a problem may occur in the storage stability of the paint.
- the acid value of the coumarone-indene resin (B) is not particularly limited, but is preferably 2.0 mgKOH / g-resin or less, and more preferably 1.0 mgKOH / g-resin or less. . When the above value is exceeded, a problem may occur in the storage stability of the paint.
- the hydroxyl value of the coumarone-indene resin (B) is not particularly limited, but is preferably 5 mgKOH / g-resin or more, more preferably 10 mgKOH / g-resin. If it is less than the above value, the adhesion of the paint may be lowered. Further, it is preferably 200 mgKOH / g-resin or less, more preferably 150 mgKOH / g-resin or less. If it exceeds the above value, the storage stability of the paint may be lowered.
- the paint composition of the present invention can contain a pigment.
- the pigment include titanium oxide, calcium carbonate, barium sulfate, talc, and carbon black. These can be used alone or in combination of two or more.
- the total amount of the pigment is preferably 50 to 500 parts by mass, and more preferably 75 to 350 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin.
- the coating composition contains a hydrocarbon solvent (C), and further contains at least one of an ester solvent or a ketone solvent (D).
- the hydrocarbon solvent (C) is preferably contained in an amount of 200 parts by mass or more, more preferably 300 parts by mass or more, relative to 100 parts by mass of the acid-modified polyolefin (A). Moreover, it is preferable that it is 3000 mass parts or less, and it is more preferable that it is 2500 mass parts or less. More preferably, it is 1800 mass parts or less. By being within the above range, excellent paint storage stability can be exhibited.
- the total amount of the ester solvent or the ketone solvent (D) is preferably 20 parts by mass or more and more preferably 50 parts by mass or more with respect to 100 parts by mass of the acid-modified polyolefin (A). Moreover, it is preferable that it is 500 mass parts or less, It is more preferable that it is 400 mass parts or less, More preferably, it is 200 mass parts or less. By being within the above range, excellent paint storage stability can be exhibited.
- hydrocarbon solvent (C) examples include aromatic hydrocarbon solvents such as toluene, xylene, Solvesso (registered trademark) 100, and alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane.
- aromatic hydrocarbon solvents such as toluene, xylene, Solvesso (registered trademark) 100
- alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane.
- xylene or cyclohexane is preferable.
- a combination of xylene, Solvesso® 100 and cyclohexane is preferred.
- ester solvent of the ester solvent or the ketone solvent (D) examples include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, and amyl acetate. Of these, ethyl acetate is preferred.
- the ketone solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone, and methyl ethyl ketone is preferable. Two or more kinds of ester solvents and ketone solvents can be combined.
- an alcohol solvent (E) to the coating composition.
- the paint storage stability can be further improved.
- blending alcohol solvent (E) it is preferable that it is 5 mass parts or more with respect to 100 mass parts of acid-modified polyolefin, More preferably, it is 10 mass parts or more. Moreover, it is preferable that it is 200 mass parts or less, More preferably, it is 150 mass parts or less.
- the alcohol solvent (E) include methanol, ethanol, normal-propyl alcohol, isopropyl alcohol, normal-butanol, isobutanol, and 2-butanol.
- the coating composition of the present invention comprises an acid-modified polyolefin (A), a coumarone / indene resin (B), a hydrocarbon solvent (C), and is further composed of at least one of an ester solvent or a ketone solvent (D).
- the coating composition of the present invention can be provided by diluting as necessary.
- the coating composition of the present invention is preferably a substantially solvent-based coating composition. That is, when the total solvent contained in the coating composition is 100% by mass, the total of the carbon solvent (C), ester solvent, ketone solvent (D) and alcohol solvent (E) is 90% by mass or more. More preferably, it is 95 mass% or more, More preferably, it is 99 mass% or more, and it may be 100 mass%. By being substantially a solvent-based coating composition, excellent water resistance and chemical resistance can be exhibited.
- the viscosity of the coating composition at the time of coating is not particularly limited, but the coating workability is good when it is within the range of 10 to 300 mPa ⁇ sec, more preferably 15 to 200 mPa ⁇ sec. Suitable for the finished appearance.
- the coating composition proposed in the present invention may contain an acrylic resin, an alkyd resin, a urethane resin, or the like as long as the effects of the present invention are not impaired.
- the liquid containing the resin was centrifuged to separate and purify an acid-modified propylene-butene copolymer grafted with maleic anhydride, (poly) maleic anhydride and a low molecular weight product. Thereafter, it was dried at 70 ° C. under reduced pressure for 5 hours to obtain an acid-modified propylene-butene copolymer (acid value 14 mg KOH / g-resin, weight average molecular weight 90,000, Tm 70 ° C.).
- the acid-modified polyolefin produced by this production example was designated as A-1.
- Production Example 2 An acid-modified propylene-butene copolymer (acid value 40 mgKOH / wt) was prepared in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 30 parts by mass and di-tert-butyl peroxide was changed to 3 parts by mass. g-resin, weight average molecular weight 90,000, Tm 70 ° C.). The acid-modified polyolefin produced by this production example was designated as A-2.
- Production Example 3 An acid-modified propylene-butene copolymer (acid value 5 mgKOH / wt) was prepared in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 3 parts by mass and di-tert-butyl peroxide was changed to 7 parts by mass. g-resin, weight average molecular weight 90,000, Tm 70 ° C.). The acid-modified polyolefin produced by this production example was designated as A-3.
- Production Example 4 An acid-modified propylene-butene copolymer (acid value 14 mgKOH / wt) was prepared in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 12 parts by mass and di-tert-butyl peroxide was changed to 3 parts by mass. g-resin, weight average molecular weight 180,000, Tm 70 ° C.). The acid-modified polyolefin produced by this production example was designated as A-4.
- Production Example 5 An acid-modified propylene-butene copolymer (acid value 14 mgKOH / wt) was prepared in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 5 parts by mass and di-tert-butyl peroxide was changed to 10 parts by mass. g-resin, weight average molecular weight 20,000, Tm 70 ° C.). The acid-modified polyolefin produced by this production example was designated as A-5.
- a solution Preparation example of acid-modified polyolefin (A) solution> A 500 ml four-necked flask equipped with a water-cooled reflux condenser and a stirrer is charged with 280 parts by weight of cyclohexane and 120 parts by weight of xylene with respect to 100 parts by weight of A-1, and the temperature is raised to 70 ° C. while stirring. A-1 solution was obtained by stirring for 1 hour.
- A-2 to A-5 were dissolved in the same manner as the A-1 solution to obtain A-2 to A-5 solutions.
- ⁇ Chlorinated polyolefin> A 500 ml four-necked flask equipped with a water-cooled reflux condenser and a stirrer was charged with 100 parts by mass of chlorinated polyolefin (A-6) having a molecular weight of 70,000 chlorine content of 21 wt%, 280 parts by mass of cyclohexane and butyl acetate. 120 parts by mass were charged, the temperature was raised to 70 ° C. with stirring, and stirring was continued for 1 hour to obtain an A-6 solution.
- A-6 chlorinated polyolefin
- coumarone / indene resin (B) solution Coumarone indene having a weight average molecular weight of 950, a softening point of 120 ° C., a hydroxyl value of 30 mgKOH / g-resin, and an acid value of 1.0 mgKOH / g-resin or less in a 500 ml four-necked flask equipped with a water-cooled reflux condenser and a stirrer 100 parts by mass of resin (B-1), 50 parts by mass of Solvesso 100, and 50 parts by mass of cyclohexane were charged and stirred at room temperature for 2 hours to obtain a B-1 solution.
- Knitlon registered trademark
- Coumarone-indene resin (B-2) having a weight average molecular weight of 160, a hydroxyl value of 50 mgKOH / g-resin, and an acid value of 1.0 mgKOH / g-resin or less was added to a 500 ml four-necked flask equipped with a water-cooled reflux condenser and a stirrer. ), 100 parts by mass, 50 parts by mass of Solvesso 100, and 50 parts by mass of cyclohexane were charged and stirred at room temperature for 2 hours to obtain a B-2 solution.
- Knit Resin registered trademark
- alkyd resin (B) derived from soybean oil and having an oil length of 41 wt%, phthalic anhydride of 42 wt%, and an acid value of 8.0 mgKOH / g-resin or less is added to a 500 ml four-necked flask equipped with a water-cooled reflux condenser and a stirrer. -3) was added in an amount of 100 parts by mass, 50 parts by mass of Solvesso 100 and 50 parts by mass of cyclohexane, and stirred at room temperature for 2 hours to obtain a B-3 solution.
- the alkyd resin (B-3) used was Alchidia (registered trademark) 1307-60-EL manufactured by DIC.
- the acid value (mgKOH / g-resin) of the acid-modified polyolefin (A) in the present invention is FT-IR (manufactured by Shimadzu Corporation, FT-IR8200PC).
- Acid value [absorbance (I) ⁇ (f) ⁇ 2 ⁇ molecular weight of potassium hydroxide ⁇ 1000 (mg) / molecular weight of succinic anhydride] Molecular weight of succinic anhydride: 100.07 Molecular weight of potassium hydroxide: 56.11
- GPC gel permeation chromatograph Alliance
- the melting point of the acid-modified polyolefin (A) in the present invention is measured at a rate of 20 ° C./minute using a differential scanning calorimeter (hereinafter DSC, manufactured by TA Instruments Japan, Q-2000). This is a value measured from the top temperature of the melting peak when the temperature is melted and cooled to resin and then melted again.
- DSC differential scanning calorimeter
- the softening point of the coumarone-indene resin (B) in the present invention was measured according to JIS K 2207 (1996).
- Example 1 The coating composition shown in Example 1 was prepared as follows. A bead mill is used until 500 parts by mass of the A-1 solution (A-1, 100 parts by mass) and 40 parts by mass of xylene and a pigment having a mass ratio shown in Table 1 are added, and the evaluation by a grindometer is 10 ⁇ m or less. To obtain a pigment dispersion. Example 1 was carried out by adding the B-1 solution to the pigment dispersion (A-1, 100 parts by mass) so that B-1 was 100 parts by mass, and then mixing 110 parts by mass of cyclohexane and 105 parts by mass of methyl ethyl ketone. The coating composition shown in FIG.
- Table 1 shows acid-modified polyolefin (A), coumarone / indene resin (B), hydrocarbon solvent (C), ester solvent, ketone solvent (D), and alcohol solvent (E).
- the coating compositions shown in Examples 2 to 8 were prepared by mixing in the same manner as in Example 1 except for mixing. The ester solvent, ketone solvent, and alcohol solvent were added to the pigment dispersion.
- Comparative Examples 1-6 Table 2 shows acid-modified polyolefin (A), coumarone / indene resin (B), hydrocarbon solvent (C), ester solvent, ketone solvent (D), and alcohol solvent (E).
- the coating compositions shown in Comparative Examples 1 to 5 were prepared by mixing them and mixing them in the same procedure as in Example 1. The ester solvent, ketone solvent, and alcohol solvent were added to the pigment dispersion. Since Comparative Example 6 did not contain the hydrocarbon-based solvent (C), the coating composition could not be prepared, and thus was not evaluated.
- Paint Stability The following items were evaluated regarding the paint stability of the paint compositions prepared in Examples or Comparative Examples. The results are shown in Tables 1 and 2.
- the coating composition was allowed to stand at ⁇ 5 ° C. and 50 ° C. for 10 days, and the appearance and viscosity of the coating composition were evaluated.
- the viscosity was measured with a Ford Cup (No. 4, 25 ° C.).
- Evaluation criteria A There was no change in appearance, and thickening occurred within 5 seconds.
- ⁇ There was no change in the appearance, and thickening occurred within 5 seconds over 5 seconds.
- ⁇ Although there was no change in appearance, it took more than 10 seconds to increase the viscosity.
- X Appearance changed and thickening required more than 10 seconds.
- a diluted coating composition Preparation of test coated plate
- the solvent composition at the time of coating was adjusted by blending 30 parts by mass of Solvesso 100 and 30 parts by mass of toluene with respect to 100 parts by mass of the coating composition obtained in Examples or Comparative Examples.
- the adjusted coating composition is referred to as a diluted coating composition.
- the polypropylene substrate was degreased with isopropyl alcohol to obtain a test plate.
- the diluted coating composition prepared above was spray-coated on a test plate so as to have a dry film thickness of 10 ⁇ m.
- the diluted paint composition surface of the test plate was spray-coated with Retan (registered trademark) PG White (trade name, manufactured by Kansai Paint Co., Ltd.) as a colored base paint so as to have a dry film thickness of 50 ⁇ m. Then, it heated for 30 minutes in 80 degreeC oven, and the test coating plate in which the laminated coating film was formed was obtained.
- Various coating film performance tests shown below were performed on the test coating plate.
- a test solution was prepared based on a test alcohol-added fuel solution specified by ISO1817.
- the test solution was 25.35 wt% of 2.2.4 trimethylpentane, 42.25 wt% of toluene, 12.68 wt% of diisobutylene, 15.0 wt% of methanol, 4.22 wt% of ethanol, and 0 of water. 0.5 wt% and 20 ppm formic acid.
- the test coated plate was immersed in this test solution at 25 ° C. for 120 minutes.
- test coated plates were air-dried at room temperature for 30 minutes, and each test coated plate was cut with a cutter so as to reach the substrate, thereby making 100 grids having a size of 1 mm ⁇ 1 mm.
- Adhesive cellophane tape was affixed to the surface, and the remaining number of cross-cut coating films after the tape was rapidly peeled off at 20 ° C. was examined. Evaluation criteria ⁇ : 100 remaining ⁇ : 99-90 remaining ⁇ : 89-41 remaining ⁇ : 40 or less remaining
- the coating composition according to the present invention contains an acid-modified polyolefin and a coumarone / indene resin, so that a coating film having excellent chemical resistance such as water resistance, gasohol resistance and fuel resistance can be formed. Therefore, it is useful as a primer for a polypropylene base material used for automobile bumpers and the like.
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Abstract
Description
酸変性ポリオレフィン(A)100質量部に対して、クマロン・インデン樹脂(B)が25~400質量部であり、
さらにエステル系溶剤、またはケトン系溶剤(D)の少なくとも一方を含むことを特徴とする塗料組成物。
本発明において酸変性ポリオレフィン(A)としては、ポリエチレン、ポリプロピレン及びプロピレン-α-オレフィン共重合体の少なくとも1種に、α,β-不飽和カルボン酸及びその酸無水物の少なくとも1種をグラフトすることにより得られるものが好ましい。
本発明においてクマロン・インデン樹脂(B)は、モノマー成分としてクマロン類、及びインデン類を主成分とするものであることが好ましい。好ましくは、クマロン類およびインデン類が、クマロン・インデン樹脂中に合計量で50質量%以上含まれるものであり、60質量%以上含まれるとより好ましい。クマロン類の具体例として、クマロンやメチルクマロン等があげられ、インデン類の具体例としては、インデンやメチルインデン等が挙げられる。クマロン類、インデン類以外のモノマー成分としては、スチレン、ビニルトルエン、ジシクロペンタジエン等が挙げられる。モノマー組成は、樹脂の用途等により適宜選択されるが、通常はクマロン類が1~80質量%、インデン類が20~95質量%程度である。またスチレンは1~20質量%含むことが好ましい。クマロン・インデン樹脂に、水酸基あるいはカルボン酸基が含まれていてもよい。
本発明の塗料組成物は、酸変性ポリオレフィン(A)、クマロン・インデン樹脂(B)、炭化水素系溶剤(C)を含み、さらにエステル系、またはケトン系溶剤(D)の少なくとも一方により構成され、必要に応じて希釈することにより、本発明の塗料組成物を提供することができる。
製造例1
1Lオートクレーブに、メタロセン触媒により重合されたプロピレン-ブテン共重合体(プロピレン成分76モル%および、1-ブテン成分24モル%)を100質量部、トルエン150質量部及び無水マレイン酸9質量部、ジ-tert-ブチルパーオキサイドを4質量部を加え、140℃まで昇温した後、更に3時間撹拌した。その後、得られた反応液を冷却後、多量のメチルエチルケトンが入った容器に注ぎ、樹脂を析出させた。その後、当該樹脂を含有する液を遠心分離することにより、無水マレイン酸がグラフト重合した酸変性プロピレン-ブテン共重合体と(ポリ)無水マレイン酸および低分子量物とを分離、精製した。その後、減圧下70℃で5時間乾燥させることにより、酸変性プロピレン-ブテン共重合体(酸価14mgKOH/g-resin、重量平均分子量90,000、Tm70℃)を得た。この製造例により作製した酸変性ポリオレフィンをA-1とした。
無水マレイン酸の仕込み量を30質量部、ジ-tert-ブチルパーオキサイドを3質量部に変更した以外は製造例1と同様にすることにより、酸変性プロピレン-ブテン共重合体(酸価40mgKOH/g-resin、重量平均分子量90,000、Tm70℃)を得た。この製造例により作製した酸変性ポリオレフィンをA-2とした。
無水マレイン酸の仕込み量を3質量部、ジ-tert-ブチルパーオキサイドを7質量部に変更した以外は製造例1と同様にすることにより、酸変性プロピレン-ブテン共重合体(酸価5mgKOH/g-resin、重量平均分子量90,000、Tm70℃)を得た。この製造例により作製した酸変性ポリオレフィンをA-3とした。
無水マレイン酸の仕込み量を12質量部、ジ-tert-ブチルパーオキサイドを3質量部に変更した以外は製造例1と同様にすることにより、酸変性プロピレン-ブテン共重合体(酸価14mgKOH/g-resin、重量平均分子量180,000、Tm70℃)を得た。この製造例により作製した酸変性ポリオレフィンをA-4とした。
無水マレイン酸の仕込み量を5質量部、ジ-tert-ブチルパーオキサイドを10質量部に変更した以外は製造例1と同様にすることにより、酸変性プロピレン-ブテン共重合体(酸価14mgKOH/g-resin、重量平均分子量20,000、Tm70℃)を得た。この製造例により作製した酸変性ポリオレフィンをA-5とした。
水冷還流凝縮器と撹拌機を備えた500mlの四つ口フラスコに、A-1を100質量部に対してシクロヘキサンを280質量部、キシレンを120質量部仕込み、撹拌しながら70℃まで昇温し、1時間撹拌することでA-1溶液を得た。
水冷還流凝縮器と撹拌機を備えた500mlの四つ口フラスコに、分子量70,000塩素含有率21wt%の塩素化ポリオレフィン(A-6)を100質量部、シクロヘキサンを280質量部および酢酸ブチルを120質量部仕込み、撹拌しながら70℃まで昇温し、撹拌を1時間続けることでA-6溶液を得た。
水冷還流凝縮器と撹拌機を備えた500mlの四つ口フラスコに、重量平均分子量950、軟化点120℃、水酸基価30mgKOH/g―resin、酸価1.0mgKOH/g-resin以下のクマロン・インデン樹脂(B-1)を、100質量部、Solvesso 100を50質量部、シクロヘキサンを50質量部仕込み、室温で2時間撹拌することでB-1溶液を得た。なお、クマロン・インデン樹脂(B-1)は日塗化学社製のニットレジン(登録商標)クマロンV-120Sを用いた。
水冷還流凝縮器と撹拌機を備えた500mlの四つ口フラスコに、大豆油由来であり、油長41wt%、無水フタル酸42wt%、酸価8.0mgKOH/g-resin以下のアルキド樹脂(B-3)を、100質量部、Solvesso 100を50質量部、シクロヘキサンを50質量部仕込み、室温で2時間撹拌することでB-3溶液を得た。なお、アルキド樹脂(B-3)はDIC社製のアルキディア(登録商標)1307-60-ELを用いた。
本発明における酸変性ポリオレフィン(A)の酸価(mgKOH/g-resin)は、FT-IR(島津製作所社製、FT-IR8200PC)を使用して、無水マレイン酸(東京化成製)のクロロホルム溶液によって作成した検量線から得られる係数(f)、酸変性ポリオレフィン溶液における無水コハク酸のカルボニル(C=O)結合の伸縮ピーク(1780cm-1)の吸光度(I)を用いて下記式により算出した値である。
酸価(mgKOH/g-resin)=[吸光度(I)×(f)×2×水酸化カリウムの分子量×1000(mg)/無水コハク酸の分子量]
無水コハク酸の分子量:100.07 水酸化カリウムの分子量:56.11
クマロン・インデン樹脂(B)の酸価は、JIS K 5601-2-1(1999)に従い測定した。
本発明における酸変性ポリオレフィン(A)およびクマロン・インデン樹脂(B)の重量平均分子量は日本ウォーターズ社製ゲル浸透クロマトグラフAlliance e2695(以下、GPC、標準物質:ポリスチレン樹脂、移動相:テトラヒドロフラン、カラム:Shodex KF-806 + KF-803、カラム温度:40℃、流速:1.0ml/分、検出器:フォトダイオードアレイ検出器(波長254nm = 紫外線))によって測定した値である。
本発明における酸変性ポリオレフィン(A)の融点は示差走査熱量計(以下、DSC、ティー・エー・インスツルメント・ジャパン製、Q-2000)を用いて、20℃/分の速度で昇温融解、冷却樹脂化して、再度昇温融解した際の融解ピークのトップ温度から測定した値である。
本発明におけるクマロン・インデン樹脂(B)の軟化点は、JIS K 2207(1996)に従い測定した。
実施例1
実施例1に示す塗料組成物は、以下の通りに作製した。A-1溶液500質量部(A-1、100質量部)に対して、キシレン40質量部、さらに表1に示す質量比の顔料を添加し、グラインドメーターによる評価が10μm以下になるまで、ビーズミルで分散することで顔料分散液を得た。顔料分散液(A-1、100質量部)に、B-1が100質量部になるようB-1溶液を加え、次いでシクロヘキサン110質量部、メチルエチルケトン105質量部を混合することで、実施例1に示す塗料組成物を得た。
酸変性ポリオレフィン(A)、クマロン・インデン樹脂(B)、炭化水素系溶剤(C)、エステル系溶剤、またはケトン系溶剤(D)、さらにはアルコール系溶剤(E)を表1に示す割合で混合し、それ以外は実施例1と同様の手順で混合することにより、実施例2~8に示す塗料組成物を作製した。エステル系溶剤、ケトン系溶剤、アルコール系溶剤は、顔料分散液に添加した。
酸変性ポリオレフィン(A)、クマロン・インデン樹脂(B)、炭化水素系溶剤(C)、エステル系溶剤、またはケトン系溶剤(D)、さらにはアルコール系溶剤(E)を表2に示す割合で混合し、それ以外は実施例1と同様の手順で混合することにより、比較例1~5に示す塗料組成物を作製した。エステル系溶剤、ケトン系溶剤、アルコール系溶剤は、顔料分散液に添加した。なお比較例6は、炭化水素系溶剤(C)を含有しないため、塗料組成物を作製できなかったため、評価を行っていない。
実施例または比較例で作製した塗料組成物の塗料安定性に関し、以下の項目について評価した。結果を表1と表2に示す。
評価基準
◎:外観に変化がなく、増粘が5秒以内に生じた。
○:外観に変化がなく、増粘が5秒を超え10秒以内に生じた。
△:外観に変化はないが、増粘に10秒超要した。
×:外観に変化が生じ、かつ増粘に10秒超要した。
実施例または比較例で得られた塗料組成物100質量部に対して、30質量部のSolvesso 100と30質量部のトルエンを配合することで、塗装時の溶剤組成に調整した。以下、調整後の塗料組成物を希釈塗料組成物と記載する。
上記通り作成した試験塗板に関し、以下の各項目について評価試験を行った。結果を表1と表2に示す。
各試験塗板の素地に達するようにカッターで切り込みを入れ、大きさ1mm×1mmの碁盤目を100個作った。その表面に粘着セロハンテープを貼着し、20℃においてそのテープを急激に剥離した後の碁盤目塗膜の残存数を調べた。
評価基準
◎:100個残存
○:99~90個残存
△:89~41個残存
×:40個以下残存
各試験塗板を40℃の温水に10日間浸漬後、塗膜表面を観察した。
評価基準
◎:外観に全く変化がなく、非常に良好である。
○:外観にほぼ変化がなく、良好である。
×:塗膜が膨潤し、フクレ等の異常が確認される。
各試験塗板を、ガソリン/エタノール=90/10重量比の試験液中に20℃で浸し、120分経過時のふくれ、剥がれの塗面状態を観察し、下記の基準で評価した。
評価基準
◎:全く異常がない。
○:直径3mm未満のふくれ、又は直径3mm未満の剥がれが生じている。
×:直径3mmを超えるふくれ、又は直径3mmを超える剥がれが生じている。
ISO1817に指定される試験用アルコール添加燃料液にもとづき、試験液を調製した。試験液は、2.2.4-トリメチルペンタンを25.35wt%、トルエンを42.25wt%、ジイソブチレンを12.68wt%、メタノールを15.0wt%、エタノールを4.22wt%、水を0.5wt%、ギ酸を20ppm含有する。試験塗板をこの試験液中に25℃で120分浸した。その後、室温で30分試験塗板を風乾させ、各試験塗板に素地に達するようにカッターで切り込みを入れ、大きさ1mm×1mmの碁盤目を100個作った。その表面に粘着セロハンテープを貼着し、20℃においてそのテープを急激に剥離した後の碁盤目塗膜の残存数を調べた。
評価基準
◎:100個残存
〇:99~90個残存
△:89~41個残存
×:40個以下残存
Claims (6)
- 酸変性ポリオレフィン(A)、クマロン・インデン樹脂(B)および炭化水素系溶剤(C)を含み、
酸変性ポリオレフィン(A)100質量部に対して、クマロン・インデン樹脂(B)が25~400質量部であり、
さらにエステル系溶剤、またはケトン系溶剤(D)の少なくとも一方を含むことを特徴とする塗料組成物。 - 酸変性ポリオレフィン(A)の酸価が5~40 mgKOH/g-resinであることを特徴とする請求項1に記載の塗料組成物。
- 酸変性ポリオレフィン(A)の重量平均分子量が20,000~180,000であることを特徴とする請求項1または2に記載の塗料組成物。
- 炭化水素系溶媒(C)が、酸変性ポリオレフィン(A)100質量部に対して、200~3000質量部含有する請求項1~3のいずれかに記載の塗料組成物。
- さらにアルコール系溶剤(E)を含むことを特徴とする請求項1~4のいずれかに記載の塗料組成物。
- 請求項1~5のいずれかに記載の塗料組成物を含有するポリオレフィン基材用プライマー塗料。
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US16/479,264 US10563082B2 (en) | 2017-01-20 | 2018-01-15 | Polyolefin coating composition |
EP18741466.9A EP3572472A4 (en) | 2017-01-20 | 2018-01-15 | POLYOLEFIN COATING COMPOSITION |
KR1020197023815A KR20190103387A (ko) | 2017-01-20 | 2018-01-15 | 폴리올레핀계 도료 조성물 |
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WO2021251100A1 (ja) * | 2020-06-10 | 2021-12-16 | 日本製紙株式会社 | 分散体組成物 |
WO2022202897A1 (ja) | 2021-03-26 | 2022-09-29 | 中国塗料株式会社 | プライマー組成物 |
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- 2018-01-15 JP JP2018563303A patent/JP6569827B2/ja active Active
- 2018-01-15 EP EP18741466.9A patent/EP3572472A4/en not_active Withdrawn
- 2018-01-15 KR KR1020197023815A patent/KR20190103387A/ko unknown
- 2018-01-15 MX MX2019008625A patent/MX2019008625A/es unknown
- 2018-01-15 WO PCT/JP2018/000758 patent/WO2018135418A1/ja unknown
- 2018-01-15 CN CN201880007691.4A patent/CN110198994A/zh active Pending
- 2018-01-15 US US16/479,264 patent/US10563082B2/en active Active
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2021054068A1 (ja) * | 2019-09-19 | 2021-03-25 | 東洋紡株式会社 | ポリオレフィン系塗料組成物 |
WO2021251100A1 (ja) * | 2020-06-10 | 2021-12-16 | 日本製紙株式会社 | 分散体組成物 |
JP7058808B1 (ja) * | 2020-06-10 | 2022-04-22 | 日本製紙株式会社 | 分散体組成物 |
WO2022202897A1 (ja) | 2021-03-26 | 2022-09-29 | 中国塗料株式会社 | プライマー組成物 |
KR20230159573A (ko) | 2021-03-26 | 2023-11-21 | 주고꾸 도료 가부시키가이샤 | 프라이머 조성물 |
Also Published As
Publication number | Publication date |
---|---|
TW201829661A (zh) | 2018-08-16 |
EP3572472A1 (en) | 2019-11-27 |
CN110198994A (zh) | 2019-09-03 |
JP6569827B2 (ja) | 2019-09-04 |
MX2019008625A (es) | 2019-12-02 |
JPWO2018135418A1 (ja) | 2019-06-27 |
US20190382611A1 (en) | 2019-12-19 |
US10563082B2 (en) | 2020-02-18 |
EP3572472A4 (en) | 2020-06-10 |
KR20190103387A (ko) | 2019-09-04 |
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