[go: up one dir, main page]

WO2018128111A1 - Résine polyoléfinique modifiée - Google Patents

Résine polyoléfinique modifiée Download PDF

Info

Publication number
WO2018128111A1
WO2018128111A1 PCT/JP2017/046355 JP2017046355W WO2018128111A1 WO 2018128111 A1 WO2018128111 A1 WO 2018128111A1 JP 2017046355 W JP2017046355 W JP 2017046355W WO 2018128111 A1 WO2018128111 A1 WO 2018128111A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
polyolefin resin
modified polyolefin
weight
modified
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/JP2017/046355
Other languages
English (en)
Japanese (ja)
Inventor
勝 神埜
由生 ▲高▼田
早川　潤一
実 矢田
高本　直輔
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.)
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
Original Assignee
Nippon Paper Industries Co Ltd
Jujo Paper Co 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 Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd filed Critical Nippon Paper Industries Co Ltd
Priority to JP2018560369A priority Critical patent/JP6943882B2/ja
Priority to TW106146640A priority patent/TWI762549B/zh
Publication of WO2018128111A1 publication Critical patent/WO2018128111A1/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
    • 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
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated 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
    • 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

Definitions

  • the present invention relates to a modified polyolefin resin.
  • Polyolefin base materials such as polypropylene are widely used for plastic molded parts, various films for food packaging materials and the like because they have excellent performance and are inexpensive. At that time, the surface of the polyolefin substrate is printed or painted for the purpose of surface protection or improvement of aesthetics.
  • the polyolefin base material is a nonpolar base material and has low surface free energy and further has crystallinity, there is a problem that ink and paint are difficult to adhere. Therefore, a technique for improving the adhesion to a polyolefin base material by adding a chlorinated polyolefin resin to ink or paint during printing or painting is widely used.
  • an object of the present invention is to provide a modified polyolefin resin having excellent chipping resistance.
  • a polyolefin resin or a modified product thereof is a copolymer in which a polymer having a predetermined (meth) acrylic acid ester unit and having a glass transition temperature of 0 ° C. or less is grafted. It has been found that the above-mentioned problems can be solved by a certain modified polyolefin resin. That is, the present invention provides the following.
  • Component (A) Polyolefin resin or modified product thereof
  • Component (B) Containing structural unit (i) derived from (meth) acrylic acid ester represented by the following general formula (I), glass transition temperature
  • a modified polyolefin resin which is a copolymer grafted with a polymer having (Tg) of 0 ° C. or lower.
  • [5] The modified polyolefin resin according to any one of [1] to [4], wherein the component (B) has a weight average molecular weight of 1,000 or more and 100,000 or less.
  • [6] The modified polyolefin resin according to any one of [1] to [5], wherein the hydroxyl value of the component (B) is from 5 mgKOH / g to 560 mgKOH / g.
  • [7] Any one of [1] to [6], wherein the weight ratio of component (A) to component (B) (component (A) / component (B)) is 20/80 or more and 80/20 or less.
  • a dispersion composition comprising the modified polyolefin resin according to any one of [1] to [8] and a dispersion medium.
  • a primer comprising the modified polyolefin resin according to any one of [1] to [8] or the dispersion composition according to [9].
  • Component (A) Polyolefin resin or modified product thereof
  • Component (B) Containing structural unit (i) derived from (meth) acrylic acid ester represented by the following general formula (I), glass transition temperature
  • a method for producing a modified polyolefin resin comprising a step of graft polymerization of a polymer having (Tg) of 0 ° C. or lower.
  • CH 2 C (R 1 ) COOR 2 (I) (In Formula (I), R 1 represents a hydrogen atom or methyl, R 2 represents a group represented by —C n H 2n + 1 , and n represents an integer of 1 to 18)
  • a modified polyolefin resin excellent in chipping resistance can be provided.
  • (meth) acrylic acid includes methacrylic acid and acrylic acid
  • (meth) acrylate includes methacrylate and acrylate.
  • the modified polyolefin resin of the present invention comprises a component (A): a polyolefin resin or a modified product thereof, a component (B): a structural unit derived from a (meth) acrylic acid ester represented by the general formula (I) (i) ) And a glass transition temperature (Tg) of 0 ° C. or lower is grafted.
  • Component (A) is a polyolefin resin or a modified product of a polyolefin resin.
  • Component (A) is a polyolefin resin or a modified product of a polyolefin resin.
  • Polyolefin resin The polyolefin resin as the component (A) is an olefin polymer.
  • the polyolefin resin as the component (A) is preferably a polyolefin resin produced using a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst, more preferably a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst.
  • metallocene catalysts can be used. Specific examples of the metallocene catalyst include a catalyst obtained by combining the components (1) and (2) described below, and (3) as necessary, and the components (1) and (2) described below. In addition, a catalyst obtained by combining (3) if necessary is preferable.
  • 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-exchangeable layered silicate.
  • -Component (3) organoaluminum compound.
  • a polyolefin resin synthesized using a metallocene catalyst is preferable as the component (A) because it has a narrow molecular weight distribution, excellent random copolymerizability, a narrow composition distribution, and a wide range of comonomers that can be copolymerized.
  • the structure of the polyolefin resin as the component (A) is not particularly limited, and 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 polymerized using a metallocene catalyst is preferable as the component (A).
  • Modified polyolefin resin Component (A) may be a modified polyolefin resin.
  • Examples and preferred examples of the polyolefin resin in the modified polyolefin resin include the above item [1-1-1. As already described in [Polyolefin Resin].
  • the type of modification is not particularly limited, and examples thereof include known modifications such as chlorination; epoxidation; hydroxylation; anhydrous carboxylic oxidation; carboxylic oxidation;
  • the modified polyolefin resin can be obtained by modifying the polyolefin resin using a known method.
  • the modified product of the polyolefin resin as the component (A) is preferably a chlorinated polyolefin resin. A method for chlorinating a polyolefin resin will be described later.
  • the chlorine content of the chlorinated polyolefin resin as the component (A) is preferably 15% by weight or more, more preferably 20% by weight or more.
  • the modified polyolefin resin is excellent in dispersibility in alcohols such as ethanol and isopropanol.
  • the upper limit of the chlorine content in the chlorinated polyolefin resin as the component (A) is preferably 40% by weight or less, more preferably 35% by weight or less.
  • the chlorine content is 40% by weight or less, the modified polyolefin resin is excellent in adhesion to a polyolefin substrate.
  • the modified product as the component (A) may be an acid-modified product obtained by modifying a polyolefin resin with an acid.
  • the acid for modification is not particularly limited, and examples thereof include ⁇ , ⁇ -unsaturated carboxylic acids and ⁇ , ⁇ -unsaturated carboxylic acid derivatives (eg, maleic acid, maleic anhydride, fumaric acid, citraconic acid, Citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, hymic anhydride, (meth) acrylic acid), and acid anhydrides of ⁇ , ⁇ -unsaturated carboxylic acids are preferred, Maleic anhydride is more preferred.
  • Component (A) is preferably a chlorinated polyolefin resin or an acid-modified chlorinated polyolefin resin.
  • the weight average molecular weight (Mw) of the component (A) is preferably 5,000 or more. When the weight average molecular weight is 5,000 or more, the cohesive strength of the resin is sufficient and the adhesion to the substrate is excellent.
  • the upper limit of the weight average molecular weight of component (A) is preferably 150,000 or less. When the weight average molecular weight is 150,000 or less, the compatibility with other resins contained in the paint or ink is good, and the adhesion to the substrate is good.
  • the weight average molecular weight can be obtained from a standard polystyrene calibration curve by gel permeation chromatography (GPC).
  • a component (B) contains the structural unit (i) derived from the (meth) acrylic acid ester represented by general formula (I).
  • CH 2 C (R 1 ) COOR 2 (I)
  • the structural unit derived from a certain monomer is a structural unit obtained when a certain monomer is used for the polymerization reaction.
  • the structural unit (i) preferably has 4 or more carbon atoms, preferably 12 or less.
  • the structural unit (i) preferably has 4 to 12 carbon atoms.
  • the chipping resistance of the modified polyolefin resin can be further improved.
  • the number of carbon atoms of the structural unit (i) is usually the same as the number of carbon atoms of the (meth) acrylic acid ester represented by the general formula (I), which is derived from the structural unit (i).
  • the structural unit (i) contained in the component (B) may be a single type or two or more types.
  • Component (B) may contain a structural unit other than the structural unit (i).
  • the structural unit other than the structural unit (i) that may be contained in the component (B) include a structural unit derived from ⁇ , ⁇ -unsaturated carboxylic acid (eg, a structure derived from (meth) acrylic acid). Units) and structural units derived from ⁇ , ⁇ -unsaturated carboxylic acid esters other than the structural unit (i) (eg, (meth) acrylic acid alkyl esters, (meth) acrylic acid hydroxyalkyl esters).
  • Component (B) has a glass transition temperature (Tg) of 0 ° C. or lower, preferably ⁇ 20 ° C. or lower, more preferably ⁇ 25 ° C. or lower, and further preferably ⁇ 30 ° C. or lower.
  • Tg glass transition temperature
  • Tg is usually ⁇ 70 ° C. or higher, preferably ⁇ 65 ° C. or higher, more preferably ⁇ 60 ° C. or higher.
  • the glass transition temperature (Tg) is obtained by using the value of each glass transition temperature when each monomer unit constituting the component (B) is a homopolymer and the weight ratio of each monomer unit in the component (B). It can be calculated by the following FOX equation.
  • the Tg of each homopolymer may be Tg listed in the Polymer Handbook (Wiley-Interscience Publication, 4th Edition, 1999) and product data.
  • the weight ratio of each monomer unit in component (B) is usually the same as the weight ratio (blending ratio) of each monomer with respect to the total monomer weight used in producing the polymer of component (B). To do.
  • component (B) and composed of n kinds of monomer units U 1 ⁇ U n, monomer units U 1 ⁇ U Tg 1 ⁇ each glass transition temperature of the homopolymer of the n Tg n and then, each of the weight fraction of monomer units U 1 ⁇ U n and W 1 ⁇ W n.
  • the 1 the sum of proportions by weight of monomer units U 1 ⁇ U n.
  • the glass transition temperature of component (B) As the glass transition temperature of component (B), the glass transition temperature measured for the polymer of component (B) as a raw material before grafting to component (A) may be used.
  • the glass transition temperature of the component (B) as a raw material can be measured using, for example, a differential scanning calorimeter (eg, “DSC6200R thermal analysis system”, supplied from Seiko Instruments Inc.).
  • the glass transition temperature of the component (B) according to the present invention is the value of each glass transition temperature when each monomer unit constituting the component (B) is a homopolymer and each unit in the component (B). It is a value calculated by the FOX equation using the weight ratio of the monomer unit.
  • Weight average molecular weight of component (B) Although there is no limitation in particular in the weight average molecular weight (Mw) of a component (B), Preferably it is 1,000 or more, More preferably, it is 3,000 or more, Preferably it is 100,000 or less, More preferably 20,000 or less.
  • the weight average molecular weight of component (B) is preferably 1,000 to 100,000, more preferably 3,000 to 20,000.
  • the weight average molecular weight of the component (B) usually coincides with the weight average molecular weight measured for the polymer of the component (B) as a raw material before being grafted to the component (A).
  • the hydroxyl value of component (B) is not particularly limited, but is preferably 5 mgKOH / g or more, preferably 560 mgKOH / g or less, more preferably 280 mgKOH / g or less, and even more preferably 168 mgKOH / g or less. It is.
  • the component (B) has a hydroxyl value of 5 mgKOH / g or more, when the modified polyolefin resin is combined with other components to form a composition (for example, a coating composition), the compatibility with the other components is good. It becomes.
  • the modified polyolefin resin has an appropriate polarity, so when the modified polyolefin resin is combined with other components to form a composition, The compatibility with the component is improved.
  • the hydroxyl value of component (B) is preferably 5 to 560 mgKOH / g, more preferably 5 to 280 mgKOH / g, and still more preferably 5 to 168 mgKOH / g.
  • Hydroxyl value X B component (B), component (B) n type (n is an integer of 1 or more) is composed of monomer units U 1 ⁇ U n of the monomer unit U 1 ⁇ U n hydroxyl value of a homopolymer of each set to X 1 ⁇ X n (mgKOH / g), the weight ratio of the monomer units U 1 ⁇ U n in component (B), respectively and Y 1 ⁇ Y n (where monomer The sum of the weight ratios of the body units U 1 to U n is 1.) and the following formula.
  • X B X 1 Y 1 + X 2 Y 2 +... X n Y n
  • the hydroxyl value of component (B) in the examples is also a value calculated by the above method.
  • the modified polyolefin resin of the present invention is a copolymer in which the component (B) is grafted to the component (A): polyolefin resin or a modified product thereof.
  • the modified polyolefin resin of the present invention may be a copolymer in which the component (B) is grafted to the component (A), and after the graft polymerization reaction for grafting the component (B) to the component (A). Further, it may be a copolymer modified with a modifying agent (for example, with chlorine and / or acid), or a copolymer not modified with a modifying agent after the graft polymerization reaction.
  • a modifying agent for example, with chlorine and / or acid
  • the polymer of component (B) is grafted to component (A).
  • the modified polyolefin resin of the present invention may be a resin produced by grafting a polymer of the component (B) as a raw material to the component (A) as a raw material by a graft polymerization reaction.
  • a resin produced by grafting a monomer for constituting the polymer (block) of the component (B) to the component (A) sequentially or simultaneously by a graft polymerization reaction may be used.
  • the modified polyolefin resin of the present invention may be a chlorinated graft modified polyolefin resin, an acid modified graft modified polyolefin resin, or an acid modified and chlorinated graft modified polyolefin resin.
  • the modified polyolefin resin of the present invention is preferably a chlorinated resin.
  • “Chlorinated resins” include resins in which component (A) is chlorinated, resins in which component (B) is chlorinated, and resins in which components (A) and (B) are chlorinated.
  • the modified polyolefin resin of the present invention is more preferably a chlorinated resin in which the component (A) is chlorinated.
  • the weight average molecular weight of the modified polyolefin resin of the present invention is not particularly limited, but is preferably 10,000 or more, more preferably 30,000 or more, preferably 200,000 or less, more preferably 150,000 or less. Adhesion is improved when the weight average molecular weight of the modified polyolefin resin is 10,000 or more. Further, when the weight average molecular weight of the modified polyolefin resin is 200,000 or less, when the modified polyolefin resin is combined with other components to form a composition, the compatibility with the other components becomes good.
  • the weight average molecular weight of the modified polyolefin resin of the present invention is preferably 10,000 to 200,000, and more preferably 30,000 to 150,000.
  • component (B) Although there is no limitation in particular in the content rate of the component (B) in the modified polyolefin resin of this invention, Preferably it is 20 weight% or more, More preferably, it is 30 weight% or more, More preferably, it is 50 weight% or more. is there. The upper limit is preferably 80% by weight or less.
  • the content of the component (B) in the modified polyolefin resin means the weight ratio of the component (B) grafted to the component (A) to the modified polyolefin resin.
  • the weight ratio (%) of the component (B) part to the modified polyolefin resin usually coincides with the blending ratio (%) of the component (B) graft-polymerized to the component (A) when producing the modified polyolefin resin ( However, the total of the blending weight of component (A) and the blending weight of component (B) is 100%.
  • the weight ratio of component (A) to component (B) in the modified polyolefin resin of the present invention is not particularly limited, but is preferably 20/80 or more, more preferably 30/70 or more, and still more preferably. It is 50/50 or more, preferably 80/20 or less.
  • the weight ratio of component (A) to component (B) in the modified polyolefin resin of the present invention is preferably 20/80 or more and 80/20 or less.
  • the production method of the modified polyolefin resin of the present invention is derived, for example, from component (A): polyolefin resin or a modified product thereof, component (B): (meth) acrylic acid ester represented by the above general formula (I) And a step of graft polymerizing a polymer containing the structural unit (i) and having a glass transition temperature (Tg) of 0 ° C. or lower.
  • R 1 represents a hydrogen atom or methyl
  • R 2 represents a group represented by —C n H 2n + 1
  • n represents an integer of 1 to 18.
  • Component (A) and Component (B) are the items [1.
  • the component (B) as a raw material represented by the general formula (I) ( A method of graft copolymerizing a polymer containing a structural unit (i) derived from a (meth) acrylic acid ester and having a glass transition temperature (Tg) of 0 ° C.
  • component (A) as a raw material
  • component (B) And a method of graft copolymerizing a (meth) acrylic acid ester represented by the above general formula (I), which is a raw material for constituting the polymer.
  • a (meth) acrylic acid ester represented by the above general formula (I) is graft copolymerized with the component (A) as a raw material
  • the (meth) acrylic acid ester represented by the above general formula (I) You may add sequentially to the component (A) as a raw material, or may be added at once. Moreover, you may add monomers other than the (meth) acrylic acid ester represented by the said general formula (I) to the component (A) as a raw material.
  • the conditions for graft polymerization are not particularly limited, and may be 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 can be performed in a short time.
  • the solution method is used, a uniform graft polymer can be obtained with few side reactions.
  • component (A) is heated and melted (heated and melted) in the presence of a radical reaction initiator to react with the component (B).
  • Component (B) 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 component (A), and preferably not lower than the melting point of component (A) and not higher than 300 ° C.
  • equipment such as a Banbury mixer, a kneader, and an extruder can be used.
  • the component (A) is dissolved in an organic solvent and then reacted with the component (B) by heating and stirring in the presence of a radical reaction initiator.
  • Component (B) may be in the form of a monomer before polymerization or in the form of a polymer after polymerization.
  • the organic solvent an aromatic hydrocarbon solvent such as toluene or xylene is preferably used.
  • the temperature during the reaction is preferably 100 to 180 ° C.
  • an organic peroxide type compound or an azonitrile is mentioned.
  • 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-butylper
  • the component (A) may be graft-polymerized as a composition containing an optional stabilizer in addition to the component (A).
  • 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 an epoxy compound that is compatible with a resin that has been modified such as chlorination is preferable. Examples of the epoxy compound include compounds having an epoxy equivalent of about 100 to 500 and having one or more epoxy groups per molecule.
  • epoxy compounds include vegetable oils having natural unsaturated groups.
  • Epoxidized vegetable oil obtained by epoxidizing with peracid such as peracetic acid (epoxidized soybean oil, epoxidized linseed oil, etc.); epoxidized unsaturated fatty acid such as oleic acid, tall oil fatty acid, soybean oil fatty acid, etc.
  • Epoxidized fatty acid esters Epoxidized alicyclic compounds such as epoxidized tetrahydrophthalate; obtained by condensing bisphenol A or polyhydric alcohol and epichlorohydrin, for example, bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl Ether, glyce Ethers such as allyl polyglycidyl ether and sorbitol polyglycidyl ether; and butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, and monoepoxy compounds represented by tert-butylphenyl glycidyl
  • One type of stabilizer may be used alone, or a combination of two or more types may be used.
  • the weight ratio of the stabilizer to the component (A) is preferably 1 to 20% by weight (in terms of solid content).
  • the method for producing the modified polyolefin resin of the present invention may include an optional step in addition to the above-described steps.
  • the optional step include a step of graft-polymerizing the component (B) to the component (A) to obtain a graft-modified polyolefin-based resin, and further modifying the graft-modified polyolefin-based resin.
  • the type of modification is not particularly limited, and examples thereof include known modifications such as chlorination; epoxidation; hydroxylation; anhydrous carboxylic oxidation; carboxylic oxidation; These modifications can be performed by known methods.
  • the production method of the present invention may include a step of chlorinating the resin at any stage of the production.
  • the polyolefin resin is chlorinated.
  • a production method for obtaining a modified polyolefin resin which is a chlorinated resin for example, a method of grafting component (B) onto component (A) and then chlorinating, a method of chlorinating polyolefin resin and component (A) And a method of grafting component (B) onto component (A) after obtaining chlorinated polyolefin resin as.
  • the chlorination method may be a known method and is not particularly limited. Examples thereof include a method in which chlorine is blown after the resin is dissolved in a chlorination solvent such as chloroform and chlorine is introduced. More specifically, the chlorination is carried out by dispersing or dissolving the resin in a medium such as water, carbon tetrachloride, or chloroform, and applying pressure or atmospheric pressure in the presence of a catalyst or under irradiation with ultraviolet light at 50 to 140 ° C. This can be done by blowing chlorine gas in the temperature range.
  • the chlorinated solvent used can be usually distilled off under reduced pressure or replaced with another organic solvent.
  • the chlorine content of the chlorinated polyolefin resin as the component (A) is preferably 15% by weight or more, more preferably 20% by weight. That's it.
  • the resulting modified polyolefin resin is excellent in dispersibility in alcohols such as ethanol and isopropanol.
  • the upper limit of the chlorine content in the chlorinated polyolefin resin as the component (A) is preferably 40% by weight or less, more preferably 35% by weight or less.
  • the chlorine content is 40% by weight or less, the resulting modified polyolefin resin is excellent in adhesion to a polyolefin substrate.
  • the modified polyolefin resin of the present invention may constitute a modified polyolefin resin composition together with other optional components.
  • the optional component include a stabilizer for suppressing the release of chlorine.
  • Stabilizers are not particularly limited.
  • epoxy compounds epoxy compounds; metal soaps such as calcium stearate and lead stearate used as stabilizers for polyvinyl chloride resins; organic metals such as dibutyltin dilaurate and dibutylmalate Compounds: Hydrotalcite compounds are exemplified, and an epoxy compound is preferable.
  • an epoxy compound is not specifically limited, For example, said [2.
  • the modified polyolefin resin composition may be in the form of a dispersion composition containing a modified polyolefin resin and a dispersion medium.
  • the “dispersion medium” includes a solvent capable of dissolving the modified polyolefin resin
  • the “dispersion composition” may be a solution of the modified polyolefin 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, n-butyl acetate; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol; ethylene glycol, Examples include glycols such as ethyl cellosolve and butyl cellosolve; water and the like.
  • the dispersion medium may be a single type or a combination of two or more types.
  • modified polyolefin resin of the present invention can be used as a metal and / or resin adhesive, primer, paint binder and ink binder.
  • the modified polyolefin resin of the present invention has good adhesion and excellent chipping resistance, and is therefore useful as a binder for automobile paint and a primer for automobile painting.
  • Part and % mean “part by weight” and “% by weight”, respectively, unless otherwise specified.
  • the following operations were performed in a normal temperature and normal pressure atmosphere unless otherwise specified.
  • Polyolefin Resin A biaxial extrusion in which a propylene random copolymer (propylene unit content: 80% by weight, ethylene unit content 20% by weight) produced using a metallocene catalyst as a polymerization catalyst is set at a barrel temperature of 400 ° C. It was supplied to a machine for thermal degradation to obtain a polypropylene resin (A5) having a weight average molecular weight of 2,000.
  • Chlorinated Polyolefin Resin 100 parts by weight of the polypropylene resin (A1) obtained in Production Example A1 was charged into a glass-lined reaction kettle. Chloroform was added thereto, and chlorine gas and oxygen gas were blown in while irradiating ultraviolet rays under a pressure of 2 kg / cm 2 , and chlorinated until the chlorine content became 32 wt%. After completion of the reaction, 6 parts by weight of 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. Then, the solvent was removed and solidified to obtain a chlorinated polypropylene resin (A1CL1) having a weight average molecular weight of 5000, which is a chlorinated polyolefin resin.
  • an epoxy compound Eposizer W-100EL, manufactured by Dainippon Ink & Chemicals, Inc.
  • Chlorinated Polyolefin Resin Chlorinated Polypropylene resin (A5CL2) having a weight average molecular weight of 2,000 as in Production Example CL1, except that the polypropylene resin (A5) obtained in Production Example A5 was used. Got.
  • Acid-Modified Polyolefin Resin 100 parts by weight of the polypropylene resin (A3) obtained in Production Example A3 is placed in a three-necked flask equipped with a stirrer, a dropping funnel, and a monomer reflux condenser tube, and 180 ° C. Completely dissolved in an oil bath. After replacing the flask with nitrogen for about 10 minutes, 4 parts by weight of maleic anhydride was added over about 5 minutes while stirring, and then 0.4 parts by weight of di-tert-butyl peroxide was added to 1 part of heptane. It melt
  • a polyolefin resin (A3M1) was obtained.
  • Example 1 (Production of acrylic polymer (B1)) After adding 2.8 parts by weight of a peroxyester peroxide (Nyper BMT-K40, manufactured by NOF Corporation) to 233 parts of toluene heated to 85 ° C. in a nitrogen atmosphere, the examples in Table 2 100 parts by weight of each acrylic monomer was added at the blending ratio described in 1 and reacted at 85 ° C. for 6 hours or longer, then cooled and cooled with an acrylic polymer having a glass transition temperature of ⁇ 66 ° C. A coalescence (B1) was obtained.
  • a peroxyester peroxide Neyper BMT-K40, manufactured by NOF Corporation
  • Example 2 An acrylic polymer having a glass transition temperature of ⁇ 33 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added in the mixing ratio described in Example 2 in Table 2. Combined (B2) was obtained. Instead of 80 parts of chlorinated polypropylene resin (A1CL1), 50 parts of acid-modified chlorinated polypropylene resin (A2M2CL1) obtained in Production Example MCL1 was used, and acrylic polymer (B1) was used in place of 20 parts. A toluene dispersion containing the modified polyolefin resin (C2) was obtained in the same manner as in Example 1 except that 50 parts of the coalescence (B2) was used.
  • a toluene dispersion containing the modified polyolefin resin (C2) was obtained in the same manner as in Example 1 except that 50 parts of the coalescence (B2) was used.
  • Acrylic polymer having a glass transition temperature of ⁇ 1 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added in the mixing ratio described in Example 3 in Table 2. Combined (B3) was obtained. Instead of 80 parts of chlorinated polypropylene resin (A1CL1), 20 parts of acid-modified chlorinated polypropylene resin (A1M2CL2) obtained in Production Example MCL2 was used, and acrylic polymer (B1) instead of 20 parts. A toluene dispersion containing the modified polyolefin resin (C3) was obtained in the same manner as in Example 1 except that 80 parts of the combined (B3) was used.
  • Acrylic polymer having a glass transition temperature of ⁇ 46 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 5 in Table 2. Combined (B5) was obtained. Instead of 80 parts of chlorinated polypropylene resin (A1CL1), 60 parts of acid-modified chlorinated polypropylene resin (A4M1CL4) obtained in Production Example MCL4 was used, and acrylic polymer (B1) instead of 20 parts. A toluene dispersion containing the modified polyolefin resin (C5) was obtained in the same manner as in Example 1 except that 40 parts of the coalesced (B5) was used.
  • Example 6 An acrylic polymer having a glass transition temperature of -43 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 6 in Table 2. Combined (B6) was obtained.
  • the chlorinated polypropylene resin (A4CL3) obtained in Production Example CL3 was used instead of the chlorinated polypropylene resin (A1CL1), and the acrylic polymer (B6) was used instead of the acrylic polymer (B1).
  • a toluene dispersion containing a modified polyolefin resin (C6) was obtained.
  • Example 7 An acrylic polymer having a glass transition temperature of ⁇ 60 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 7 in Table 2. Combined (B7) was obtained.
  • Modified polyolefin resin in the same manner as in Example 1 except that 60 parts of chlorinated polypropylene resin (A1CL1) was used and 40 parts of acrylic polymer (B7) was used instead of 20 parts of acrylic polymer (B1). A toluene dispersion containing (C7) was obtained.
  • Example 8 An acrylic polymer having a glass transition temperature of ⁇ 66 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 8 in Table 2. Combined (B8) was obtained. Instead of 80 parts of the chlorinated polypropylene resin (A1CL1), 70 parts of the chlorinated polypropylene resin (A5CL2) obtained in Production Example CL2 was used, and an acrylic polymer (B1) instead of 20 parts. B8) A toluene dispersion containing the modified polyolefin resin (C8) was obtained in the same manner as in Example 1 except that 30 parts were used.
  • Acrylic polymer having a glass transition temperature of ⁇ 24 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 9 in Table 2. Combined (B9) was obtained.
  • a toluene dispersion containing C8) was obtained.
  • Example 10 An acrylic polymer having a glass transition temperature of ⁇ 66 ° C. was prepared in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the blending ratio described in Example 10 in Table 2. Combined (B10) was obtained. Instead of 80 parts of chlorinated polypropylene resin (A1CL1), 60 parts of acid-modified polypropylene resin (A3M1) obtained in Production Example M1 was used, and acrylic polymer (B10) instead of 20 parts of acrylic polymer (B1). ) A toluene dispersion containing the modified polyolefin resin (C10) was obtained in the same manner as in Example 1 except that 40 parts were used.
  • a toluene dispersion containing the modified polyolefin resin (C10) was obtained in the same manner as in Example 1 except that 40 parts were used.
  • Tg Glass transition temperature
  • ⁇ Hydroxyl value of component (B) (acrylic polymer) (mgKOH / g)>
  • the hydroxyl value in the case where each monomer used in producing the polymer of the component (B) that has been identified is a homopolymer, and the blending ratio of each monomer used in producing the component (B) And calculated by the method described above.
  • ⁇ Paint stability> The toluene dispersions of the modified polypropylene resins obtained in Examples and Comparative Examples were blended with toluene to prepare a toluene dispersion having a solid content of 20%. 15 parts by weight of the prepared toluene dispersion (solid content 20 wt%) is added to 90 parts by weight of urethane resin (manufactured by Hitachi Chemical Co., Ltd., solid content 30 wt%), and the mixture is stirred for 10 minutes with a shaker and allowed to stand at room temperature for 1 day. The solution properties after placement were observed, and the paint stability (compatibility of the compounded resin) was visually judged from the separated state of the solution.
  • ⁇ Chip resistance test> The painted plate is cooled in a low-temperature room cooled to -20 ° C, and the test plate is fixed vertically to the test plate mounting part of the stepping stone testing machine (Suga Test Instruments Co., Ltd., JA-400 type) at an angle of 90 ° from the horizontal. Then, 100 g of No. 7 crushed stone was sprayed for 5 seconds at an air pressure of 5 kgf / cm 2 to scratch the test plate. After that, the painted plate is washed with water and dried, and the cellophane adhesive tape is adhered to the coated surface, peeled off with one end of the tape, and the paint film lifted by chipping is removed, and the degree of peeling scratches is evaluated according to the following criteria. did.
  • 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.
  • the modified polyolefin resin of the example is superior in chipping resistance as compared with Comparative Example 1. Moreover, it turns out that the modified polyolefin resin of an Example has no problem in the adhesiveness to the polypropylene which is a nonpolar base material, and stability when it is set as a resin dispersion liquid or a coating material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

L'invention concerne une résine polyoléfinique modifiée présentant une excellente résistance à l'écaillage. La résine polyoléfinique modifiée est un copolymère dans lequel un composant (B) est greffé sur un composant (A), le composant (A) étant une résine polyoléfinique ou un produit modifié à base de celle-ci, et le composant (B) étant un polymère qui comprend un motif structural (i) dérivé d'un ester d'acide (méth)acrylique et qui est représenté par la formule générale (I) ci-dessous, et qui présente une température de transition vitreuse (Tg) égale ou inférieure à 0 °C. (I) CH2=C(R1)COOR2 (dans la formule (I), R1représente un atome d'hydrogène ou un groupe méthyle, R2 un groupe représenté par -CnH2n+1 et n un nombre entier de 1 à 18.)
PCT/JP2017/046355 2017-01-05 2017-12-25 Résine polyoléfinique modifiée Ceased WO2018128111A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2018560369A JP6943882B2 (ja) 2017-01-05 2017-12-25 変性ポリオレフィン系樹脂
TW106146640A TWI762549B (zh) 2017-01-05 2017-12-29 改質聚烯烴系樹脂

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017000449 2017-01-05
JP2017-000449 2017-01-05

Publications (1)

Publication Number Publication Date
WO2018128111A1 true WO2018128111A1 (fr) 2018-07-12

Family

ID=62789506

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/046355 Ceased WO2018128111A1 (fr) 2017-01-05 2017-12-25 Résine polyoléfinique modifiée

Country Status (3)

Country Link
JP (1) JP6943882B2 (fr)
TW (1) TWI762549B (fr)
WO (1) WO2018128111A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020209080A1 (fr) * 2019-04-11 2020-10-15 東洋紡株式会社 Composition de résine aqueuse
CN113429679A (zh) * 2021-07-20 2021-09-24 汕头市三马塑胶制品有限公司 一种新型绿色环保高熔体强度聚丙烯及其制备方法
JP7058808B1 (ja) 2020-06-10 2022-04-22 日本製紙株式会社 分散体組成物
WO2024135629A1 (fr) * 2022-12-22 2024-06-27 株式会社レゾナック Élastomère styrénique modifié et procédé de production d'élastomère styrénique modifié

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58173113A (ja) * 1982-04-05 1983-10-12 Dainippon Ink & Chem Inc 塗料用樹脂組成物
JPH10158447A (ja) * 1996-11-28 1998-06-16 Honda Motor Co Ltd ポリオレフィン用プライマー組成物
JP2002338877A (ja) * 2001-05-22 2002-11-27 Nippon Paper Industries Co Ltd ポリオレフィン系樹脂用プライマー組成物
JP2009040920A (ja) * 2007-08-09 2009-02-26 Seiko Pmc Corp 変性ポリオレフィン樹脂水性分散体組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3242595B2 (ja) * 1997-04-30 2001-12-25 トヨタ自動車株式会社 水性プライマー塗料組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58173113A (ja) * 1982-04-05 1983-10-12 Dainippon Ink & Chem Inc 塗料用樹脂組成物
JPH10158447A (ja) * 1996-11-28 1998-06-16 Honda Motor Co Ltd ポリオレフィン用プライマー組成物
JP2002338877A (ja) * 2001-05-22 2002-11-27 Nippon Paper Industries Co Ltd ポリオレフィン系樹脂用プライマー組成物
JP2009040920A (ja) * 2007-08-09 2009-02-26 Seiko Pmc Corp 変性ポリオレフィン樹脂水性分散体組成物

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020209080A1 (fr) * 2019-04-11 2020-10-15 東洋紡株式会社 Composition de résine aqueuse
JPWO2020209080A1 (fr) * 2019-04-11 2020-10-15
CN113748167A (zh) * 2019-04-11 2021-12-03 东洋纺株式会社 水性树脂组合物
CN113748167B (zh) * 2019-04-11 2023-05-26 东洋纺株式会社 水性树脂组合物
JP7616049B2 (ja) 2019-04-11 2025-01-17 東洋紡エムシー株式会社 水性樹脂組成物
US12312459B2 (en) 2019-04-11 2025-05-27 Toyobo Mc Corporation Aqueous resin composition
JP7058808B1 (ja) 2020-06-10 2022-04-22 日本製紙株式会社 分散体組成物
CN113429679A (zh) * 2021-07-20 2021-09-24 汕头市三马塑胶制品有限公司 一种新型绿色环保高熔体强度聚丙烯及其制备方法
WO2024135629A1 (fr) * 2022-12-22 2024-06-27 株式会社レゾナック Élastomère styrénique modifié et procédé de production d'élastomère styrénique modifié

Also Published As

Publication number Publication date
JP6943882B2 (ja) 2021-10-06
TW201831587A (zh) 2018-09-01
TWI762549B (zh) 2022-05-01
JPWO2018128111A1 (ja) 2019-11-07

Similar Documents

Publication Publication Date Title
CN108699178B (zh) 改性聚烯烃树脂
JP7322207B2 (ja) 塩素化ポリオレフィン系樹脂組成物
JP7368245B2 (ja) 塩素化ポリオレフィン樹脂及びその製造方法
JP6976260B2 (ja) 変性ポリオレフィン系樹脂
JP6943882B2 (ja) 変性ポリオレフィン系樹脂
JP7265483B2 (ja) 変性ポリオレフィン樹脂組成物及びその製造方法
JP2022179555A (ja) 樹脂組成物及びその用途
CN111770962B (zh) 树脂组合物
JP3898636B2 (ja) バインダー樹脂組成物と製造方法及びその用途
US6555621B1 (en) Binder resin composition and process for the production thereof
JP4473500B2 (ja) バインダー樹脂組成物及びその用途
JP3045498B2 (ja) バインダ―樹脂組成物及びその製造方法
JP2000007979A (ja) ポリオレフィン用塗料樹脂組成物及びその製造方法
JP7581185B2 (ja) 変性ポリオレフィン樹脂組成物
JP2006282928A (ja) ポリオレフィン系樹脂用コーティング組成物

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: 17890564

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018560369

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17890564

Country of ref document: EP

Kind code of ref document: A1