Classifications

• • 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
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
  • C08F8/20—Halogenation
  • C08F8/22—Halogenation by reaction with free halogens
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/14—Copolymers of propene
  • C08L23/147—Copolymers of propene with monomers containing atoms other than carbon or hydrogen
• • 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
  • C09D123/02—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 not modified by chemical after-treatment
  • C09D123/10—Homopolymers or copolymers of propene
  • C09D123/14—Copolymers of propene
  • C09D123/147—Copolymers of propene with monomers containing other atoms than carbon or hydrogen atoms
• • 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
  • C09D123/28—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 reaction with halogens or compounds containing halogen
• • 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
  • C09D151/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/08—Homopolymers or copolymers of acrylic acid esters

Definitions

• the present invention relates to a resin composition.
• Polyolefin substrates such as polypropylene have excellent performance and are inexpensive. For this reason, polyolefin base materials are widely used for plastic molded parts, various films for food packaging materials, and the like. When a polyolefin base material is used, the surface of the polyolefin base material is often printed or painted for the purpose of surface protection or aesthetic improvement.
• the polyolefin substrate is a nonpolar substrate, has low surface free energy, and has crystallinity. Therefore, the polyolefin base material has a problem that ink and paint are difficult to adhere. In view of such a problem, a technique for improving adhesion to a polyolefin base material by adding a chlorinated polyolefin resin to ink or paint during printing or painting is widely used.
• a plastic molded product such as a polyolefin base material is often used as a member attached to an automobile outer plate part or a member of home appliances.
• a primer containing a chlorinated polyolefin resin or the like is applied to a plastic molded product before the top coating for the purpose of improving the adhesion between the top coating film and the molded product.
• the coating method described in Patent Document 1 coats a primer not only on a plastic molded product but also on an automobile outer plate that is a metal. Therefore, when a coating film having a certain thickness is formed on the automobile outer plate portion, the top coating layer is reduced by the amount corresponding to the primer layer.
• the primer layer is inferior in resistance to chipping of the coating film by flipping stones (chipping resistance), so that there is a problem that the chipping resistance of the entire coated portion is lowered.
• electrodeposition coating can be cited as a paint that is frequently used for automobile outer plate parts. Since the electrodeposition coating process utilizes the difference in polarity between the object to be coated and the paint, the paint used for electrodeposition coating needs to have a relatively high polarity. For this reason, the electrodeposited surface is highly polar and it is desired to increase the amount of the polar functional group of the primer resin. However, generally, when the amount of the polar functional group is increased, there is a problem that the solution properties are deteriorated and the practical use becomes difficult.
• An object of the present invention is to provide a resin composition that is a raw material of a primer that can form a coating film that is excellent in solution stability, adhesion to a nonpolar substrate, and excellent in chipping resistance.
• the present inventors have derived from a (meth) acrylate ester having a functional group at least at the terminal and a number average molecular weight of 1,000 to 20,000 in the modified polyolefin resin. It has been found that the above-mentioned problems can be solved by mixing a polymer containing the structural unit of the present invention, and the present invention has been completed. That is, the present inventors provide the following [1] to [8].
• [1] A resin composition containing the following component A and the following component B.
• Component A Modified polyolefin resin.
• Component B a structural unit derived from a (meth) acrylic acid ester represented by the following general formula (1) having a functional group at least at the terminal and having a number average molecular weight of 1,000 to 20,000 (i) ).
• (1): CH 2 C (R 1 ) COOR 2 (In the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a group represented by —C n H 2n + 1 , and n represents an integer of 1 to 18.)
• [2] The resin composition according to [1], wherein the component A is a modified polyolefin resin modified with the following component C.
• Component C (meth) acrylic acid ester
• the structural unit (i) is derived from a (meth) acrylic acid ester having 4 to 12 carbon atoms in the compound represented by the general formula (1)
• [4] The resin composition according to any one of [1] to [3], wherein the component C is a (meth) acrylic acid ester having 4 to 12 carbon atoms.
• [5] The resin composition according to any one of [1] to [4], wherein the component A is a chlorinated polyolefin resin.
• a resin composition that is a raw material of a primer that can form a coating film that is excellent in solution stability, adhesion to a nonpolar substrate, and excellent in chipping resistance.
• (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid
• (meth) acrylic modification is a generic term for acrylic modification and methacrylic modification.
• the resin composition of the present invention comprises component A: a modified polyolefin resin, component B: a functional group at least at the terminal, and a number average molecular weight of 1,000 to 20,000, represented by general formula (1)
• the polymer containing the structural unit (i) derived from the (meth) acrylic acid ester represented is contained.
• the resin composition of the present invention may be a resin composition in which component B is mixed with component A. After mixing component B with component A, it is further modified with a modifier (for example, with chlorine and / or acid). A modified resin composition may be used.
• the resin composition of the present invention contains component A, it provides a resin composition that is a raw material of a primer that can form a coating film that is excellent in adhesion to a nonpolar substrate and also excellent in chipping resistance. Can do. Moreover, since the resin composition of this invention contains the component B, it is excellent in solution stability.
• the resin composition of the present invention preferably uses a chlorinated resin.
• chlorinated resin includes a resin in which component A is chlorinated, a resin in which component B is chlorinated, and a resin in which component A and component B are chlorinated.
• the resin composition of the present invention is more preferably a resin in which the component (A) is chlorinated.
• Component A is a modified polyolefin resin. Since the resin composition of the present invention contains a modified polyolefin resin, a resin composition serving as a raw material for a primer that can form a coating film that has excellent adhesion to a nonpolar substrate and excellent chipping resistance. Can be provided.
• the polyolefin resin may be an olefin polymer.
• the polyolefin resin is preferably a polyolefin resin using a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst, and a polypropylene resin, or propylene and ⁇ , using a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst.
• polystyrene resin obtained by copolymerizing olefins (eg, ethylene, butene, 3-methyl-1-butene, 3-methyl-1-heptene) is more preferable, and a propylene-based random copolymer using a metallocene catalyst as a polymerization catalyst.
• olefins eg, ethylene, butene, 3-methyl-1-butene, 3-methyl-1-heptene
• a propylene-based random copolymer using a metallocene catalyst as a polymerization catalyst.
• Polymers are more preferred, and polypropylene, ethylene-propylene copolymers, propylene-butene copolymers, or ethylene-propylene-butene copolymers using a metallocene catalyst as the polymerization catalyst are even more preferred.
• the resulting polyolefin resin has a narrow molecular weight distribution, excellent random copolymerizability, a narrow composition distribution, and a wide range of comonomer that can be copolymerized.
• the propylene-based random copolymer refers to a polyolefin resin obtained by random copolymerization of polypropylene, propylene, and ⁇ -olefin, such as polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, Examples thereof include an ethylene-propylene-diene copolymer and an ethylene-propylene-butene copolymer.
• the (co) polymer constituting the polyolefin resin may be a single type or a combination of a plurality of (co) polymers.
• a known metallocene catalyst can be used.
• the catalyst obtained by combining the following component (1) and component (2), and also a component (3) as needed is mentioned.
• the metallocene catalyst is preferably a catalyst obtained by combining the following component (1) and component (2) and, if necessary, component (3).
• Component (1) a metallocene complex that is a transition metal compound of Groups 4 to 6 in the periodic table having at least one conjugated five-membered ring ligand.
• Component (2) Ion exchange layered silicate.
• Component (3) an organoaluminum compound.
• the structure of the polyolefin resin may be any of an isotactic structure, an atactic structure, a syndiotactic structure and the like that can be taken by a normal polymer compound.
• a polyolefin resin having an isotactic structure that can be used when a metallocene catalyst is used is preferable.
• the propylene constituent unit content is preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more.
• adhesion adhesion to the propylene substrate can be improved.
• the propylene constituent unit content of the polyolefin resin may be a raw material usage ratio or a value calculated by NMR analysis. However, these values usually match.
• Modification Component A is a modified polyolefin resin.
• modification include known modifications such as chlorination; epoxidation; hydroxylation; anhydrous carboxylic oxidation; carboxylic oxidation; (meth) acryl modification.
• the modified polyolefin resin can be prepared by modifying the polyolefin resin using a known method.
• the modified polyolefin resin is preferably a modified polyolefin resin modified with Component C: (meth) acrylic acid ester, more preferably a modified polyolefin resin modified with (meth) acrylic acid ester having 4 to 12 carbon atoms.
• (meth) acrylic acid esters include 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Is mentioned.
• denaturation operation using the (meth) acrylic acid ester of polyolefin resin is mentioned later.
• the weight ratio of resin to component C is preferably 10/90 to 90/10, more preferably 30/70 to 80/20, and even more preferably 50/50 to 70/30. It is.
• the weight ratio of the resin to the component C can be calculated by the amount of the component C used relative to the resin.
• the “resin” used herein refers to a resin used for a modification reaction with Component C, such as a polyolefin resin itself or an acid-modified chlorinated polyolefin resin.
• the modified polyolefin resin may be an acid-modified product obtained by modifying a polyolefin resin with a carboxylic acid.
• the carboxylic acid is not particularly limited.
• ⁇ , ⁇ -unsaturated carboxylic acid and derivatives of ⁇ , ⁇ -unsaturated carboxylic acid eg, maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride
• the carboxylic acid is preferably an ⁇ , ⁇ -unsaturated carboxylic acid anhydride or (meth) acrylic acid, more preferably maleic anhydride or (meth) acrylic acid.
• the acid content is preferably 1.0 to 20% by weight, more preferably 2.0 to 15% by weight, still more preferably 2.5 to 10% by weight. It is.
• the acid content can be measured by a known method. For example, it can be determined by an alkali titration method.
• the modified polyolefin resin may be a chlorinated polyolefin resin obtained by chlorinating a polyolefin resin.
• the chlorine content is preferably 10% by weight or more, and more preferably 15% by weight or more.
• the resulting modified polyolefin resin has excellent dispersibility in various solvents including alcohols such as ethanol and isopropyl alcohol.
• the upper limit of the chlorine content is preferably 40% by weight or less.
• the resulting modified polyolefin resin has excellent adhesion to a polyolefin substrate. If the chlorine content is within this range, the polarity of the modified polyolefin resin increases, and it is presumed that the modified polyolefin resin tends to exhibit a linear structure due to steric repulsion between chlorine atoms. Therefore, it is estimated that the resin composition will be excellent in dispersibility in various organic solvents and adhesion to the substrate.
• the chlorine content can be measured based on JIS-K7229 (1995).
• the modified polyolefin resin may be a modified polyolefin resin obtained by modifying a polyolefin resin with a plurality of types of modifying materials.
• a modified polyolefin resin for example, a modified polyolefin resin subjected to at least two modification treatments of the above (meth) acryl modification, carboxyl oxidation, and chlorination can be given.
• the modified polyolefin resin is a modified polyolefin resin modified with a plurality of types of modified materials, the plurality of modifications may be performed at once or separately.
• a case will be described in which after modification with an acid, chlorination treatment is performed, and (meth) acryl modification is further performed.
• the polyolefin resin is modified with acid.
• a method of modifying the polyolefin resin with an acid a known method can be used.
• a method of adding an acid and a radical reaction initiator for melting and modifying a polyolefin resin can be mentioned.
• the reaction apparatus is not particularly limited, and for example, the modification reaction may be performed using an extruder.
• the acid-modified polyolefin resin is chlorinated.
• a chlorination method a known method can be used. For example, after dissolving the acid-modified polyolefin resin in a chlorine-based solvent such as chloroform, a method of introducing chlorine gas and introducing chlorine can be used. More specifically, the chlorination is carried out by dispersing or dissolving the acid-modified polyolefin resin in a medium such as water, carbon tetrachloride, or chloroform, and in the presence of a catalyst or under irradiation with ultraviolet light, under pressure or atmospheric pressure, 50 to This can be done by blowing chlorine gas in a temperature range of 140 ° C.
• the chlorinated solvent can usually be distilled off under reduced pressure, or may be replaced with another organic solvent.
• acid-modified and chlorinated acid-modified chlorinated polyolefin resin is (meth) acryl-modified.
• the (meth) acryl modification can be prepared, for example, by copolymerizing component C with an acid-modified chlorinated polyolefin resin.
• Component C may be added sequentially to the acid-modified chlorinated polyolefin resin or may be added at once. Further, monomers other than Component C may be added to the acid-modified chlorinated polyolefin resin.
• the copolymerization can be performed by a known method such as a melting method or a solution method.
• the melting method is advantageous in that the operation is simple and the reaction time is short.
• the solution method there can be obtained a modified polyolefin resin which has few side reactions and is uniformly graft-polymerized.
• the acid-modified chlorinated polyolefin resin is heated and melted (heated and melted) in the presence of a radical reaction initiator to react with the component C.
• Component C may be in the form of a monomer before polymerization or in the form of a polymer after polymerization.
• the temperature for heating and melting may be not lower than the melting point of the acid-modified chlorinated polyolefin resin, and is preferably not lower than the melting point of the acid-modified chlorinated polyolefin resin and not higher than 300 ° C.
• equipment such as a Banbury mixer, a kneader, and an extruder can be used.
• the acid-modified chlorinated polyolefin resin is dissolved in an organic solvent, and then reacted with the component C by heating and stirring in the presence of a radical reaction initiator.
• Component C may be in the form of a monomer before polymerization or in the form of a polymer after polymerization.
• an aromatic hydrocarbon solvent such as toluene or xylene is preferably used.
• the temperature during the reaction is preferably 100 to 180 ° C.
• Examples of the radical reaction initiator used in the melting method and the solution method include organic peroxide compounds and azonitriles.
• Examples of the organic peroxide compounds include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, 2,5-dimethyl-2,5- Di (tert-butylperoxy) hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis (tert-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (tert -Butylperoxy) -cyclohexane, cyclohexanone peroxide, tert-butylperoxybenzoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate,
• the acid-modified chlorinated polyolefin resin may be modified in a form containing an optional stabilizer.
• optional stabilizers for example, epoxy compounds; metal soaps such as calcium stearate and lead stearate, which are used as stabilizers for polyvinyl chloride resins; organometallic compounds such as dibutyltin dilaurate and dibutylmalate Hydrotalcite compounds.
• the epoxy compound is not particularly limited, but is preferably an epoxy compound that is compatible with a resin that has been modified such as chlorination.
• an epoxy compound having an epoxy equivalent of about 100 to 500 and having one or more epoxy groups per molecule can be mentioned.
• an epoxy compound for example, an epoxidized vegetable oil (epoxidized soybean oil, epoxidized linseed oil, etc.) obtained by epoxidizing a vegetable oil having a natural unsaturated group with a peracid such as peracetic acid; oleic acid , Epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acids such as tall oil fatty acid and soybean oil fatty acid; epoxidized alicyclic compounds such as epoxidized tetrahydrophthalate; bisphenol A or polyhydric alcohol and epichlorohydrin Obtained ethers such as bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl
• the weight ratio of the stabilizer to the acid-modified chlorinated polyolefin resin is preferably 1 to 20% by weight (in terms of solid content).
• the lower limit of the weight average molecular weight (Mw) of component A is preferably 20,000 or more.
• the weight average molecular weight is 20,000 or more, the cohesive force of the modified polyolefin resin is sufficient, and the resin composition has excellent adhesion to the substrate.
• the upper limit becomes like this.
• it is 200,000 or less.
• the weight average molecular weight is 200,000 or less, the compatibility with other resins different from the component A contained in the coating material is good, and the resin composition has excellent adhesion to the substrate.
• One embodiment of the weight average molecular weight of component A is preferably 20,000 to 200,000.
• the weight average molecular weight can be obtained from a standard polystyrene calibration curve by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the weight average molecular weight of component A usually coincides with the weight average molecular weight measured for the chlorinated polyolefin resin before the modification operation.
• Component B is a structural unit derived from a (meth) acrylic acid ester represented by the general formula (1) having a functional group at least at the terminal and having a number average molecular weight of 1,000 to 20,000 (i) ). Since the resin composition of this invention contains the component B, it is excellent in solution stability.
• (1): CH 2 C (R 1 ) COOR 2 (In general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a group represented by —C n H 2n + 1 , and n represents an integer of 1 to 18.)
• the structural unit derived from a certain monomer means a structural unit obtained when a certain monomer is used for the polymerization reaction.
• the (meth) acrylic acid ester represented by the general formula (1) has 4 to 12 carbon atoms, a coating film having better chipping resistance can be formed when a primer made of a resin composition is used. Therefore, it is preferable.
• Component B contains the structural unit (i) derived from the (meth) acrylic acid ester represented by the general formula (1).
• Component B is a structural unit (ii) derived from (meth) acrylic acid ester having 4 to 12 carbon atoms in the compound represented by general formula (1) (hereinafter also referred to as structural unit (ii))
• the content of the structural unit (ii) in Component B is preferably 40% by weight or more, and more preferably 60% by weight or more.
• the primer which consists of a resin composition comes to hold
• the content of the structural unit (ii) is a (meth) acrylic acid ester represented by the general formula (1) with respect to the total monomer weight used in preparing the polymer, and carbon It usually corresponds to the weight percentage of monomers having 4 to 12 atoms.
• the structural unit (i) may be a single structural unit or two or more structural units.
• Component B may include a structural unit other than the structural unit (i) (hereinafter also referred to as “other structural unit”).
• Other structural units include, for example, structural units derived from ⁇ , ⁇ -unsaturated carboxylic acids (eg, structural units derived from (meth) acrylic acid), ⁇ , ⁇ -unsaturated units other than structural unit (i). Examples include a structural unit derived from a saturated carboxylic acid ester (eg, (meth) acrylic acid hydroxyalkyl ester) and a structural unit derived from an aromatic compound having an unsaturated bond (eg, divinylbenzene).
• Examples of the functional group possessed by the polymer include a carboxy group, a hydroxyl group, an alkoxysilyl group, an amide group, and a thiol group.
• the polymer may have only one kind of these functional groups or may have two or more kinds. By having these functional groups, the affinity with the electrodeposition coating surface is increased, and the adhesion force when the resin composition is used is improved.
• a known method can be used as a method for introducing a functional group into at least the terminal of the polymer.
• a method of polymerizing (meth) acrylate using a thiol having at least one functional group in the molecule and an appropriate radical initiator, or a reversible addition-cleavage chain using a reagent having a functional group The method of performing transfer (RAFT) polymerization is mentioned.
• RAFT transfer
• a method for introducing a carboxy group as a functional group will be described.
• a thiol having at least one carboxy group in the molecule and a suitable radical initiator are used, a thiol-ene reaction proceeds between the thiol having a carboxy group and a (meth) acrylate ester, A carboxy group derived from thiols is introduced at the end of the (meth) acrylic acid ester polymer.
• thiols having at least one functional group in the molecule include ⁇ -mercaptopropionic acid (thiolactic acid), ⁇ -mercaptopropionic acid, 2,3-dimercaptopropionic acid, thioglycolic acid, and o-mercaptobenzoic acid.
• thiosalicylic acid m-mercaptobenzoic acid, p-mercaptobenzoic acid, thiomalic acid, thiol carbonic acid, o-thiocoumaric acid, ⁇ -mercaptobutanoic acid (mercaptobutyric acid), ⁇ -mercaptobutanoic acid, ⁇ -mercaptobutanoic acid Carboxyl group-containing thiols such as thiol histidine and 11-mercaptoundecanoic acid; mercaptomethanol, 1-mercaptoethanol, 1-mercaptopropanol, 1-mercapto-2,3-propanediol, 1-mercapto-2-butanol, 1 -Mercapto-2,3- Butanediol, 1-mercapto-3,4-butanediol, 1-mercapto-3,4,4'-butanetriol, 2-mercapto-3-butanol, 2-mercapto-3,4-butaned
• Examples of the radical reaction initiator used together with thiols having at least one functional group in the molecule include organic peroxide compounds and azonitriles.
• Examples of the organic peroxide compounds include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, 2,5-dimethyl-2,5- Di (tert-butylperoxy) hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis (tert-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (tert -Butylperoxy) -cyclohexane, cyclohexanone peroxide, tert-butylperoxybenzoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-
• Component B is preferably a polymer having functional groups introduced at both ends.
• a method for introducing a functional group into both ends of the polymer a known method can be used. For example, a (meth) acrylic acid ester using an initiator having a functional group and a (meth) acrylic acid ester having an unsaturated carbon-carbon double bond (hereinafter also referred to as “functional group-containing (meth) acrylic acid ester”). And a method of performing reversible addition-fragmentation chain transfer (RAFT) polymerization using a reagent having a functional group.
• RAFT reversible addition-fragmentation chain transfer
• the number average molecular weight (Mn) of Component B is 1,000 to 20,000, preferably 1,500 to 15,000, more preferably 2,000 to 10,000.
• Mn number average molecular weight
• the size of the component B molecule is small. Therefore, the amount of entropy change when mixed with Component A is increased, and the compatibility is improved. If the molecular weight of component B is greater than 20,000, the above effects may not be obtained. On the other hand, if the molecular weight of component B is less than 1,000, the adhesion to the substrate may be reduced.
• the weight ratio of component A to component B in the resin composition is preferably 90/10 to 10/90, more preferably 90/10 to 20/80, and still more preferably 90 / 10 to 50/50.
• the resin composition of the present invention may contain other optional components in addition to Component A and Component B.
• a stabilizer for suppressing detachment of chlorine can be mentioned.
• Stabilizers include, for example, epoxy compounds; metal soaps such as calcium stearate and lead stearate used as stabilizers for polyvinyl chloride resins; organometallic compounds such as dibutyltin dilaurate and dibutylmalate; hydro Examples include talcite compounds.
• the stabilizer is preferably an epoxy compound.
• the epoxy compound include an epoxy compound exemplified as an optional stabilizer that may be included in the modification of the polyolefin resin or the chlorinated polyolefin resin. Among these, an epoxy compound that is compatible with the chlorinated modified polyolefin resin is preferable. Only 1 type may be used for a stabilizer and it may use 2 or more types together.
• the resin composition may be in the form of a dispersion resin composition containing a dispersion medium together with component A and component B.
• the “dispersion medium” includes a solvent capable of dissolving the modified polyolefin resin
• the “dispersion resin composition” may be a solution of the resin composition.
• dispersion medium examples include aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aliphatic hydrocarbons such as hexane, heptane, and octane; acetone, methyl ethyl ketone, and methyl isobutyl ketone.
• Ketones such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol: ethylene glycol, Examples include glycols such as ethyl cellosolve and butyl cellosolve; and water.
• the dispersion medium may be a single type or a combination of two or more types.
• the resin composition of the present invention can be used as a metal and / or resin adhesive, primer, paint binder, ink binder, and the like. Especially, since the resin composition of this invention can provide the primer which has favorable adhesiveness and can form the coating film which is excellent in chipping resistance, it is useful as a binder for automobile paints and a primer for automobile paints.
• the present invention will be described in detail with reference to examples.
• the following examples are for explaining the present invention preferably and are not intended to limit the present invention.
• the measuring methods such as a physical-property value, are the measuring methods described above.
• parts are based on weight unless otherwise specified.
• Chip resistance test The painted plate was cooled in a low temperature room cooled to -20 ° C. A painted plate cooled to an angle of 90 ° from the horizontal is fixed vertically to the test plate mounting part of the stepping stone tester (Suga Test Instruments Co., Ltd., model JA-400), and 100g of No. 7 crushed stone with air pressure of 5kgf / cm 2 was sprayed for 5 seconds to scratch the test plate. Thereafter, the painted plate was washed with water and dried, and a cellophane adhesive tape was adhered to the coated surface. The film was peeled off by holding one end of the tape, the coating film lifted by chipping was removed, and the degree of peeling scratches was evaluated according to the following criteria.
• the evaluation of peeling scratches was performed within a frame of 70 mm length x 70 mm width of the impacted part.
• the peeled area ratio per evaluation area is 0.0% or more and less than 0.7%.
• the peeled area ratio per evaluation area is 0.7% or more and less than 1.2%.
• the peeled area ratio per evaluation area is 1.2% or more and less than 3.5%.
• D Inferior.
• the peeled area ratio per evaluation area is 3.5% or more.
• an epoxy compound (Eposizer W-100EL, manufactured by Dainippon Ink & Chemicals, Inc.) is added as a stabilizer, and supplied to a vented extruder equipped with a solvent removal suction part on the screw shaft part. Solvent was then solidified to obtain an acid-modified chlorinated polyolefin resin as an acid-modified chlorinated polypropylene resin.
• the obtained acid-modified chlorinated polyolefin resin had a weight average molecular weight of 110,000, a maleic anhydride content of 4% by weight, and a chlorine content of 17% by weight.
• the reaction was carried out to obtain a modified polyolefin resin (A-1).
• the weight average molecular weight of the modified polyolefin resin (A-1) modified with a low molecular weight compound can be said to be substantially the same as the weight average molecular weight of the acid-modified chlorinated polyolefin resin.
• an epoxy compound (Eposizer W-100EL, manufactured by Dainippon Ink & Chemicals, Inc.) is added as a stabilizer, and supplied to a vented extruder equipped with a solvent removal suction part on the screw shaft part. Solvent was then solidified to obtain an acid-modified chlorinated polyolefin resin as an acid-modified chlorinated polypropylene resin.
• the obtained acid-modified chlorinated polyolefin resin had a weight average molecular weight of 200,000, a maleic anhydride content of 10% by weight, and a chlorine content of 40% by weight.
• the reaction was carried out to obtain a modified polyolefin resin (A-2).
• the weight average molecular weight of the modified polyolefin resin (A-2) modified with a low molecular weight compound can be said to be substantially the same as the weight average molecular weight of the acid-modified chlorinated polyolefin resin.
• an epoxy compound (Eposizer W-100EL, manufactured by Dainippon Ink & Chemicals, Inc.) is added as a stabilizer, and supplied to a vented extruder equipped with a solvent removal suction part on the screw shaft part. Solvent was then solidified to obtain an acid-modified chlorinated polyolefin resin as an acid-modified chlorinated polypropylene resin.
• the obtained acid-modified chlorinated polyolefin resin had a weight average molecular weight of 110,000, a maleic anhydride content of 4% by weight, and a chlorine content of 17% by weight.
• Table 1 lists the (modified) polyolefin resins produced in Production Examples 1 to 4.
• Example 1 Resin composition
• the prepared dispersion resin composition was evaluated for the stability of the resin dispersion and the stability of the paint, and a test piece was prepared, and an adhesion test, a gasohol resistance test, and a chipping test were performed. The evaluation results are also shown in Table 3.
• Examples 2 to 3 and Comparative Examples 1 to 3 Resin compositions
• a dispersed resin composition was prepared in the same manner as in Example 1 except that the components listed in Table 3 were used.
• the prepared dispersion resin composition was evaluated for the stability of the resin dispersion and the stability of the paint, and a test piece was prepared, and an adhesion test, a gasohol resistance test, and a chipping test were performed. The evaluation results are also shown in Table 3.
• Example 4 Resin composition
• 20 parts of the polymer (B-1) produced in Production Example 5 to 80 parts of the modified polyolefin resin (A-3) produced in Production Example 3, 100 parts of the resin composition was glass-lined.
• the reaction kettle was charged. After adding chloroform and fully dissolving the resin at a temperature of 110 ° C. under a pressure of 2 kgf / cm 2 , 2 parts of azobisisobutyronitrile as a radical generator was added, and the pressure in the kettle was adjusted to 2 kgf / cm 2 . Chlorination was performed by blowing chlorine gas while controlling.
• the prepared dispersion resin composition was evaluated for the stability of the resin dispersion and the paint stability, and a test piece was prepared and subjected to an adhesion test, a gasohol resistance test, and a chipping test.
• the evaluation results are also shown in Table 3.
• Example 5 Resin composition
• a dispersed resin composition was prepared in the same manner as in Example 1 except that the components listed in Table 3 were used.
• the prepared dispersion resin composition was evaluated for the stability of the resin dispersion and the stability of the paint, and a test piece was prepared, and an adhesion test, a gasohol resistance test, and a chipping test were performed. The evaluation results are also shown in Table 3.
• test piece was prepared as follows.
• the dispersions obtained in Examples and Comparative Examples were adjusted to a solid content concentration of 30% by weight, coated on a polypropylene substrate, and dried at 80 ° C. for 5 minutes. Thereafter, a two-component urethane paint was applied and dried at 80 ° C. for 30 minutes to prepare a test piece (painted plate).

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