WO2014157624A1 - Polymère, son procédé de production et composition de résine contenant ledit polymère - Google Patents

Polymère, son procédé de production et composition de résine contenant ledit polymère Download PDF

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Publication number
WO2014157624A1
WO2014157624A1 PCT/JP2014/059135 JP2014059135W WO2014157624A1 WO 2014157624 A1 WO2014157624 A1 WO 2014157624A1 JP 2014059135 W JP2014059135 W JP 2014059135W WO 2014157624 A1 WO2014157624 A1 WO 2014157624A1
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polymer
resin composition
monomer
group
monomer unit
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PCT/JP2014/059135
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English (en)
Japanese (ja)
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哲史 元田
大輔 加登
恵 平田
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株式会社クラレ
アミリス， インコーポレイティド
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Priority to JP2015508763A priority Critical patent/JPWO2014157624A1/ja
Priority to CN201480017895.8A priority patent/CN105121482A/zh
Priority to KR1020157026353A priority patent/KR102167198B1/ko
Publication of WO2014157624A1 publication Critical patent/WO2014157624A1/fr

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    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/22—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having three or more carbon-to-carbon double bonds

Definitions

  • the present invention relates to a polymer containing a monomer unit derived from farnesene and a method for producing the same. Moreover, this invention relates to the resin composition containing the polymer containing the monomer unit derived from farnesene, the hardened
  • Patent Document 1 discloses a composition comprising polyisoprene having a (meth) acryloyl group in the molecule, a monofunctional (meth) acrylate monomer and a radical polymerization initiator, and further having a secondary amino group in the molecule.
  • a curable resin composition containing a hindered amine compound that does not have is described.
  • Patent Document 2 describes an epoxy resin, a curing agent, and a thermosetting resin composition containing a specific amount of an epoxy group in the molecule and an epoxidized polybutadiene having a specific number average molecular weight.
  • Patent Documents 3 and 4 describe polymers of ⁇ -farnesene. However, practical applications have not been sufficiently studied, and ⁇ -farnesene having a polymerizable functional group has not been studied. There are no studies on polymers.
  • the present invention has been made in view of the above circumstances, and provides a cured product having a low viscosity, a high curing speed, excellent curing shrinkage, and excellent strength, flexibility, low moisture permeability and transparency.
  • the polymer which can be manufactured, and its manufacturing method are provided.
  • the present invention also provides a resin composition having a low viscosity, a high curing rate, excellent curing shrinkage, and capable of giving a cured product having excellent strength, flexibility, low moisture permeability and transparency, and curing the resin composition.
  • a polymer having a polymerizable functional group introduced into a polymer having a monomer unit derived from farnesene has strength, flexibility, low moisture permeability and transparency. It was found that a cured product excellent in the properties of the polymer can be obtained, and that the polymer has a low viscosity, a high curing rate, and excellent curing shrinkage, and the first aspect of the present invention has been completed.
  • the present inventors have obtained a cured product in which a polymer having a polymerizable functional group introduced into a polymer having a monomer unit derived from farnesene is excellent in strength, flexibility, low moisture permeability and transparency. Further, it was found that the resin composition containing this polymer has a low viscosity, a high curing speed, and excellent curing shrinkage, and completed the second and fourth embodiments of the present invention.
  • the present inventors provide a polymer having a polymerizable functional group containing a monomer unit derived from farnesene and a polymerizable functional group containing a monomer unit derived from a conjugated diene compound having 12 or less carbon atoms. It has been found that a resin composition containing a polymer that does not have a specific ratio has a low viscosity and can give a cured product having excellent strength, flexibility, hardness and transparency. Four aspects were completed.
  • the gist of the present invention is the following [1] to [9].
  • [1] A polymer having a polymerizable functional group containing the monomer unit (a1) derived from farnesene as the monomer unit constituting the polymer.
  • the method for producing a polymer according to [1] comprising a step (2) of introducing a group.
  • the polymer (A) according to [1], the monomer (D), and the polymerization initiator (C) are contained, and the mass ratio of the polymer (A) to the monomer (D) [( A) / (D)] is 0.01 to 99, and 0.1 to 20 parts by mass of the polymerization initiator (C) with respect to 100 parts by mass in total of the polymer (A) and the monomer (D).
  • a resin composition to contain to contain.
  • the polymer (F) contains a monomer unit derived from a conjugated diene compound (f1) having 12 or less carbon atoms and has a polymerizable functional group, and the polymer (A) and the polymer (F The resin composition according to any one of [3] to [5], wherein a mass ratio [(A) / (F)] to 0.01) is 0.01 to 100.
  • a cured product obtained by curing the resin composition according to any one of [3] to [6].
  • a polymer capable of giving a cured product having a low viscosity, a high curing speed, excellent curing shrinkage, and excellent strength, flexibility, low moisture permeability and transparency And a manufacturing method thereof.
  • the second and fourth aspects of the present invention it is possible to provide a cured product having a low viscosity, a high curing rate, excellent curing shrinkage, and excellent strength, flexibility, low moisture permeability and transparency.
  • the resin composition which can be provided can be provided.
  • cured material or the said resin composition can be provided.
  • a resin composition that can give a cured product having a low viscosity and excellent in strength, flexibility and transparency, a cured product obtained by curing the resin composition, and the cured product.
  • an optical pressure-sensitive adhesive containing the resin composition can be provided.
  • the polymer of the present invention includes a monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer and has a polymerizable functional group.
  • the farnesene-derived monomer unit (a1) may be an ⁇ -farnesene-derived monomer unit or a ⁇ -farnesene-derived monomer unit represented by the following formula (I).
  • a monomer unit derived from ⁇ -farnesene is preferable. Note that ⁇ -farnesene and ⁇ -farnesene may be used in combination.
  • Examples of the polymerizable functional group include (meth) acryloyl group, epoxy group, oxetanyl group, vinyl ether group, alkoxysilyl group, (meth) acrylamide group, styrene group, maleimide group, lactone group, lactam group, sulfide group. , A thietane group, an acetonide group, and a thiourea group. Among these, at least one selected from a (meth) acryloyl group, an epoxy group, an oxetanyl group, a vinyl ether group, and an alkoxysilyl group is preferable, and a (meth) acryloyl group Groups are more preferred. These functional groups may have a substituent.
  • “(meth) acryloyl” means “acryloyl or methacryloyl”. In the present specification, “(meth) acryl” means “acryl or methacryl”.
  • the monomer unit constituting the polymer (A) may be composed only of the farnesene-derived monomer unit (a1) or derived from a monomer other than the farnesene-derived monomer unit (a1) and farnesene. It may consist of the monomer unit (a2). That is, the polymer (A) may be obtained by polymerizing only farnesene, or may be a copolymer of farnesene and a monomer other than farnesene.
  • examples of the monomer unit (a2) derived from a monomer other than farnesene include a monomer unit derived from a conjugated diene compound and an aromatic vinyl compound. Can do.
  • the conjugated diene compound is preferably a conjugated diene compound having 12 or less carbon atoms.
  • the conjugated diene compound having 12 or less carbon atoms include butadiene, isoprene, 2,3-dimethyl-butadiene, 2-phenyl-butadiene, 1,3 -Pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene , Myrcene, chloroprene and the like. Of these, isoprene and butadiene are more preferred.
  • These conjugated diene compounds may be used individually by 1 type, and may use 2 or more types together.
  • aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2- Aromatic vinyl compounds such as vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-aminoethyl styrene, vinyl pyridine, 4-methoxy styrene, monochlorostyrene, dichlorostyrene,
  • a monomer unit (a2) derived from a monomer other than farnesene a monomer derived from a monomer other than farnesene in the copolymer (a1) and a monomer other than farnesene
  • the proportion of the monomer unit (a2) derived from a monomer other than farnesene relative to the total of the units (a2) is the viewpoint of reducing the viscosity of the polymer, the viewpoint of improving the curing rate, and the good elongation of the cured product. From the viewpoint of maintaining characteristics and flexibility, it is preferably 1 to 99% by mass, more preferably 1 to 80% by mass, still more preferably 1 to 70% by mass, and even more preferably 1 to 50% by mass.
  • the number average molecular weight (Mn) of the polymer (A) of the present invention is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, more preferably 8,000 to 500,000, and 15,000 to 45. Is more preferable, 15,000 to 300,000 is still more preferable, and 20,000 to 200,000 is still more preferable.
  • Mn of a polymer (A) is the value calculated
  • the number average molecular weight (Mn) in this specification is a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
  • the melt viscosity at 38 ° C. of the polymer (A) of the present invention is preferably from 0.1 to 3000 Pa ⁇ s, more preferably from 0.6 to 3000 Pa ⁇ s, more preferably from 0.6 to 2800 Pa ⁇ s. 5 to 2600 Pa ⁇ s is more preferable, and 1.5 to 800 Pa ⁇ s is still more preferable.
  • the melt viscosity (38 ° C.) of the polymer is within the above range, the polymer can be uniformly applied to the surface to be coated, so that the coating property is improved.
  • the melt viscosity (38 ° C.) of the polymer is a value determined by the method described in Examples described later.
  • the molecular weight distribution (Mw / Mn) of the polymer (A) of the present invention is preferably 1.0 to 8.0, more preferably 1.0 to 5.0, and still more preferably 1.0 to 3.0. When Mw / Mn is within the above range, the resulting polymer (A) has less variation in viscosity.
  • the glass transition temperature of the polymer (A) of the present invention varies depending on the bonding mode (microstructure), other farnesene-derived monomers, and the amount of monomers other than farnesene used as necessary. -90 to 0 ° C is preferable, and -90 to -10 ° C is more preferable. Within the above range, a flexible cured product can be obtained, and the step following ability and the impact absorbing ability can be improved in an adhesive used for a laminated structure such as a liquid crystal screen.
  • the number of polymerizable functional groups per molecular chain of the polymer (A) of the present invention is preferably 1 to 150, more preferably 1.5 to 75, and still more preferably 1.5 to 30.
  • the number of polymerizable functional groups per molecular chain is within the above range, the viscosity of the polymer (A) can be reduced, the curing rate can be improved, and further curing can be achieved. Shrinkage can be kept low.
  • the number of polymerizable functional groups per molecular chain is expressed by the following formula from the number average molecular weight (Mn) of the polymer (A) and the functional group equivalent (g / eq) of the polymer (A). Calculated.
  • the functional group equivalent is “molecular weight of polymer per functional group”.
  • the functional group equivalent when the polymerizable functional group is a methacryloyl group is referred to as “methacryloyl equivalent”, which means “molecular weight of polymer per methacryloyl group”.
  • the functional group equivalent can be calculated based on the reaction rate of the modifier, or can be determined using various analytical instruments such as infrared spectroscopy and nuclear magnetic resonance spectroscopy.
  • the polymer (A) used in the present invention may be used alone or in combination of two or more kinds of the polymers (A) having different monomer units, molecular weights and functional groups. Also good.
  • Ratio of common logarithm of melt viscosity (Pa ⁇ s) at 38 ° C. and number average molecular weight (Mn) of polymer (A) of the present invention [ordinary logarithm of melt viscosity at 38 ° C./number average molecular weight (Mn) ] Is preferably 0.000060 or less, preferably 0.000055 or less, and more preferably 0.000050 or less.
  • the ratio of the common logarithm value of the melt viscosity at 38 ° C. and the number average molecular weight is within the above range, it becomes possible to uniformly apply the polymer to the surface to be coated. Will be better.
  • the step (1) for preparing the unmodified polymer will be described later, and here, the step (2) for mainly introducing a polymerizable functional group into the unmodified polymer will be described.
  • an unmodified polymer is prepared by polymerizing farnesene and, if necessary, monomers other than farnesene, and maleic anhydride is added to the unmodified polymer.
  • a method of reacting a compound for grafting such as 2-hydroxyethyl methacrylate, and then reacting a compound having a polymerizable functional group such as 2-hydroxyethyl methacrylate is preferable.
  • Examples of the compound for grafting the unmodified polymer include unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, itaconic anhydride; maleic acid, fumaric acid Unsaturated carboxylic acid such as acid, citraconic acid and itaconic acid; unsaturated carboxylic acid ester such as maleic acid ester, fumaric acid ester, citraconic acid ester and itaconic acid ester; maleic acid amide, fumaric acid amide, citraconic acid amide and itaconic acid Unsaturated carboxylic acid amides such as acid amides; unsaturated carboxylic acid imides such as maleic acid imides, fumaric acid imides, citraconic acid imides, itaconic acid imides; maleimides, vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, etc.
  • Examples of the compound having a polymerizable functional group include (meth) acrylic acid; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, (Meth) acrylates such as dipentaerythritol monohydroxyacrylate; 2-hydroxyethyl vinyl ether, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, N- (2-hydroxyethyl) maleimide, 4-ethenylphenol and the like can be mentioned.
  • the position at which the polymerizable functional group is introduced may be the polymerization terminal or the side chain of the polymer.
  • the said functional group may combine 1 type (s) or 2 or more types.
  • a hydroxyl group, a carboxyl group, and a hydroxyl group are added to the unmodified polymer by an addition reaction with the living end of the unmodified polymer obtained by living anionic polymerization of farnesene.
  • Living anionic polymerization initiators for living anionic polymerization of farnesene include, for example, methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium, phenyl lithium, stilbene lithium and the like.
  • a compound such as diisopropenylbenzene or dibenzyltoluene that reacts with an organic alkali metal reagent to give a polyfunctional organic alkali metal reagent may be used in combination.
  • the compound for introducing an atomic group having at least one functional group at the living terminal include cyclic ethers such as epoxide and oxetane; cyclic amines such as pyrrolidine; cyclic sulfides such as ethylene sulfide.
  • the said functional group may combine 1 type (s) or 2 or more types.
  • an unmodified polymer was prepared by polymerizing farnesene and, if necessary, monomers other than farnesene, and this unmodified polymer was epoxidized. Thereafter, a method of reacting the above-described compound having a polymerizable functional group may be mentioned.
  • Examples of the compound for epoxidizing the unmodified polymer include peracids such as peracetic acid and perbenzoic acid.
  • Examples of the compound having a polymerizable functional group include carboxylic acids such as acrylic acid and methacrylic acid.
  • the position at which the polymerizable functional group is introduced may be the polymerization terminal or the side chain of the polymer.
  • the said functional group may combine 1 type (s) or 2 or more types.
  • an antiaging agent suitable for the unmodified polymer or the modified polymer is used for the purpose of suppressing molecular weight reduction, discoloration and gelation due to deterioration. You may combine.
  • the said anti-aging agent may use together 1 type, or 2 or more types.
  • the addition amount of the antioxidant is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the unmodified polymer or modified polymer.
  • the unmodified polymer which is a raw material of the polymer (A) of the present invention can be produced by an emulsion polymerization method or a method described in International Publication No. 2010/027463 and International Publication No. 2010/027464. Among these, an emulsion polymerization method or a solution polymerization method is preferable, and a solution polymerization method is more preferable.
  • an emulsion polymerization method for obtaining an unmodified polymer a known method can be applied. For example, a predetermined amount of farnesene is emulsified and dispersed in the presence of an emulsifier, and emulsion polymerization is performed using a radical polymerization initiator.
  • a radical polymerization initiator for example, a long chain fatty acid salt or rosin acid salt having 10 or more carbon atoms is used. Specific examples include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
  • water is usually used, and it may contain a water-soluble organic solvent such as methanol and ethanol as long as the stability during polymerization is not inhibited.
  • a water-soluble organic solvent such as methanol and ethanol
  • the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, and hydrogen peroxide.
  • a chain transfer agent can also be used to adjust the molecular weight of the unmodified polymer.
  • chain transfer agent examples include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, ⁇ -terpinene, ⁇ -methylstyrene dimer, and the like.
  • the emulsion polymerization temperature can be appropriately selected depending on the type of radical polymerization initiator to be used, but is usually preferably 0 to 100 ° C, more preferably 0 to 60 ° C.
  • the polymerization mode may be either continuous polymerization or batch polymerization. The polymerization reaction can be stopped by adding a polymerization terminator.
  • polymerization terminator examples include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine, and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.
  • an antioxidant may be added as necessary.
  • unreacted monomers are removed from the obtained latex as necessary, and then a salt such as sodium chloride, calcium chloride, potassium chloride is used as a coagulant, and nitric acid, sulfuric acid, etc.
  • the unmodified polymer is coagulated while adjusting the pH of the coagulation system to a predetermined value by adding an acid, and then the unmodified polymer is recovered by separating the dispersion solvent. Next, after washing with water and dehydration, drying is performed to obtain an unmodified polymer.
  • latex and an extending oil that has been made into an emulsified dispersion may be mixed and recovered as an oil-modified unmodified polymer.
  • the monomer is polymerized in the presence of a polar compound as desired using a Ziegler catalyst, a metallocene catalyst, or an anionically polymerizable active metal in a solvent.
  • a polar compound as desired using a Ziegler catalyst, a metallocene catalyst, or an anionically polymerizable active metal in a solvent.
  • the anion-polymerizable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium . Of these, alkali metals and alkaline earth metals are preferable, and alkali metals are particularly preferable.
  • alkali metals organic alkali metal compounds are more preferably used.
  • the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Aromatic hydrocarbons such as toluene and xylene are exemplified.
  • organic alkali metal compound examples include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium; dilithiomethane, dilithionaphthalene Polyfunctional organolithium compounds such as 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like. Among these, an organic lithium compound is preferable, and an organic monolithium compound is more preferable.
  • the amount of the organic alkali metal compound used is appropriately determined depending on the required molecular weight of the unmodified polymer, but is 0.01 to 7 masses with respect to 100 mass parts of the total amount of farnesene and monomers other than farnesene as necessary. Part is preferred.
  • the organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, dibenzylamine and the like.
  • the polar compound is used to adjust the microstructure of the farnesene moiety in anionic polymerization without deactivating the reaction.
  • ether compounds such as dibutyl ether, tetrahydrofuran, ethylene glycol diethyl ether; tetramethylethylenediamine, trimethylamine, etc. Tertiary amines; alkali metal alkoxides, phosphine compounds and the like.
  • the polar compound is preferably used in an amount of 0.01 to 1000 molar equivalents relative to the organoalkali metal compound.
  • the temperature of the polymerization reaction is usually in the range of ⁇ 80 to 150 ° C., preferably 0 to 100 ° C., more preferably 10 to 90 ° C.
  • the polymerization mode may be either batch or continuous.
  • the polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator.
  • the unmodified polymer can be isolated by pouring the obtained polymerization reaction solution into a poor solvent such as methanol to precipitate the unmodified polymer, or washing the polymerization reaction solution with water, separating, and drying.
  • the resin composition according to the second aspect of the present invention is a polymer comprising the monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer according to the first aspect of the present invention, that is, a polymer. It is a resin composition containing the polymer (A) having a group.
  • the polymer (A) in the first aspect of the present invention has a low viscosity, a high curing rate, and an excellent curing shrinkage.
  • the resin composition using the polymer (A) has strength, flexibility, low moisture permeability and A cured product having excellent transparency can be provided.
  • the resin composition in the second aspect of the present invention includes a polymer (A) having a polymerizable functional group containing a monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer,
  • the monomer (D) and the polymerization initiator (C) are contained, and the mass ratio [(A) / (D)] of the polymer (A) and the monomer (D) is 0.01 to 99.
  • a resin composition containing 0.1 to 20 parts by mass of the polymerization initiator (C) with respect to 100 parts by mass in total of the polymer (A) and the monomer (D) is preferable.
  • the polymer (A) used in the second embodiment of the present invention contains a monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer and has a polymerizable functional group.
  • This polymer (A) is the same as the polymer in the first aspect of the present invention, has a low viscosity, a high curing rate, and is excellent in curing shrinkage.
  • the content of the polymer (A) in the resin composition in the second embodiment of the present invention is preferably 1 to 99% by mass, more preferably 2 to 98% by mass, further preferably 5 to 95% by mass. 90% by mass is even more preferable, and 15 to 85% by mass is even more preferable.
  • a cured product excellent in strength, flexibility, low moisture permeability and transparency can be provided.
  • the monomer (D) used in the present invention is not particularly limited as long as it can be polymerized by a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator, but a polymer for obtaining a uniformly cured product.
  • a monomer copolymerizable with the functional group (A) is preferred.
  • Examples of the monomer (D) include compounds having a (meth) acryloyl group, an epoxy group, an oxetanyl group, a vinyl ether group, and an alkoxysilyl group in the molecule.
  • Specific compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, butyl ethoxy (meth) acrylate, butyl ethyl (meth) acrylate, and 2-ethylhexyl (meth).
  • dicyclopentanyloxyethyl (meth) acrylate dicyclopentenyloxyethyl (meth) acrylate, 1,9-nonanediol diacrylate, n-Butyl acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and phenoxyethyl (meth) acrylate are preferred. These may be used alone or in combination of two or more.
  • the mass ratio [(A) / (D)] of the polymer (A) and the monomer (D) is 0.01 to 99, preferably 0.1 to 99, more preferably 0.2 to 99. Preferably, 0.2 to 10 is more preferable, and 0.2 to 5 is still more preferable. When the mass ratio [(A) / (D)] is within the above range, a cured product excellent in flexibility and low cure shrinkage is obtained reflecting the physical properties of the polymer (A).
  • Examples of the polymerization initiator (C) used in the present invention include a photopolymerization initiator that initiates a polymerization reaction by irradiation with active energy rays such as ultraviolet rays, and a thermal polymerization initiator that initiates a polymerization reaction by heat. From the viewpoint that the resin is cured by irradiation with time and a cured product can be obtained without altering the base material, a photopolymerization initiator is preferable, and a photopolymerization initiator that initiates a polymerization reaction by ultraviolet irradiation is more preferable. preferable.
  • Examples of the photopolymerization initiator include a cationic photopolymerization initiator and a radical polymerization initiator.
  • Examples of the cationic photopolymerization initiator include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, metallocene compounds, and the like.
  • a cationic photopolymerization initiator of an aromatic diazonium salt “P-33 (trade name)” (manufactured by ADEKA Corporation) and the like are known.
  • Known examples of cationic photopolymerization initiators of aromatic iodonium salts include “Rhodorsil Photo Initiator 2074 (trade name)” (manufactured by Rhodia Co., Ltd.), “Irgacure 250 (trade name)” (manufactured by BASF Corporation), and the like. Yes.
  • radical photopolymerization initiators include acetophenone, benzophenone, alkylphenone, acylphosphine oxide, benzoin, ketal, anthraquinone, disulfide, thioxanthone, thiuram, and fluoroamine. It is done. Of these, alkylphenone or acylphosphine oxide radical photopolymerization initiators are preferred. Examples of the alkylphenone radical photopolymerization initiators include hydroxyalkylphenone and aminoalkylphenone.
  • Hydroxylphenone radical photopolymerization initiators include “DAROCUR 1173 (trade name)” (2-hydroxy-2-methyl-1-phenylpropan-1-one), “Irgacure 184 (trade name)” (1 -Hydroxycyclohexyl phenyl ketone), “Irgacure 2959 (trade name)” (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one) and the like It is done.
  • aminoalkylphenone radical photopolymerization initiators examples include “Irgacure 907 (trade name)” (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), “Irgacure 369”. (Trade name) ”(2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone) and the like.
  • Acylphosphine oxide radical photopolymerization initiators include “LUCIRIN TPO (trade name)” (2,4,6-trimethylbenzoyldiphenylphosphine oxide), “Irgacure 819 (trade name)” (bis (2,4 , 6-trimethylbenzoyl) -phenylphosphine oxide) (all manufactured by BASF Corporation). Of these, hydroxyalkylphenone-based radical photopolymerization initiators are preferred, and 2-hydroxy-2-methyl-1-phenylpropan-1-one is more preferred. These may be used alone or in combination of two or more.
  • the content of the polymerization initiator (C) is 0.1 to 20 parts by mass, and 0.5 to 15 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the monomer (D).
  • the amount is preferably 1 to 10 parts by mass, and more preferably 1.5 to 6 parts by mass.
  • the content of the polymerization initiator (C) is within the above range, it is preferable in terms of curing speed and mechanical properties.
  • the resin composition in the second aspect of the present invention contains a hindered amine compound (E) as necessary in order to further improve the heat resistance and weather resistance of the resin composition and the cured product obtained therefrom. Also good.
  • a hindered amine type compound (E) it is preferable to use the hindered amine type compound which does not have a secondary amino group in a molecule
  • Examples of the hindered amine compound (E) having no secondary amino group in the molecule include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] Methyl] butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, methyl 1,2,2,6,6-pentamethyl-4- Piperidyl sebacate, tetrakis 1,2,3,4-butanetetracarboxylate (1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,2,6,6-pentamethyl-4 Piperidyl methacrylate and the like.
  • the content of the hindered amine compound (E) is preferably 0.01 to 10 parts by mass, preferably 0.5 to 7 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the monomer (D). 1 to 4 parts by mass is more preferable.
  • the content of the hindered amine compound (E) is within the above range, it is preferable in terms of improving the heat resistance and improving the mechanical properties of the cured product.
  • the method for producing the resin composition in the second aspect of the present invention is not particularly limited.
  • the resin composition in the second aspect of the present invention has a melt viscosity at 38 ° C. of preferably 15 Pa ⁇ s or less, more preferably 12 Pa ⁇ s or less, and still more preferably 10 Pa ⁇ s or less.
  • the melt viscosity of the resin composition is within the above range, it is possible to uniformly apply the resin composition to the surface to be coated, and it is easy to prevent air bubbles from being mixed. Become.
  • the melt viscosity of the resin composition is a value determined by the method described in Examples described later.
  • the cured product according to the second aspect of the present invention is obtained by curing the resin composition according to the second aspect of the present invention.
  • the resin composition according to the second aspect of the present invention is irradiated with energy rays.
  • energy rays for curing ultraviolet rays are preferable.
  • the ultraviolet ray source include a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a microwave excimer lamp, and the like.
  • an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere in which the oxygen concentration is lowered is preferable.
  • the irradiation atmosphere temperature is preferably 10 to 200 ° C.
  • the UV irradiation amount is preferably 200 to 10,000 mJ / cm 2 .
  • optical pressure sensitive adhesive contains the cured product or resin composition according to the second aspect of the present invention, and is suitable for electronic devices such as smartphones, liquid crystal displays, and organic EL displays. Can be used.
  • additives can be appropriately added as necessary without departing from the object of the present invention.
  • the additive include a tackifier, a plasticizer, a pigment, a colorant, an anti-aging agent, and an ultraviolet absorber.
  • the resin composition according to the third aspect of the present invention is a polymer comprising the monomer unit (a1) derived from farnesene as the monomer unit constituting the polymer of the first aspect of the present invention, that is, the polymer.
  • the resin composition has a mass ratio [(A) / (B)] of the polymer (A) to the polymer (B) of 0.01 to 100.
  • the polymer (A) used in the third aspect of the present invention includes a monomer unit (a1) derived from farnesene as a monomer unit constituting the polymer and has a polymerizable functional group.
  • This polymer (A) is the same as the polymer in the first aspect of the present invention, has a low viscosity, a high curing rate, and is excellent in curing shrinkage.
  • the content of the polymer (A) in the resin composition in the third embodiment of the present invention is preferably 1 to 99% by mass, more preferably 2 to 98% by mass, still more preferably 5 to 95% by mass. 90% by mass is even more preferable, and 15 to 85% by mass is even more preferable.
  • a cured product excellent in strength, flexibility, low moisture permeability and transparency can be provided.
  • the polymer (B) contains a monomer unit (b1) derived from a conjugated diene compound having 12 or less carbon atoms and does not have a polymerizable functional group.
  • the conjugated diene compound having 12 or less carbon atoms as the monomer unit (b1) include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3- Examples include pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, and chloroprene. Of these, isoprene and butadiene are more preferred.
  • These conjugated diene compounds may be used individually by 1 type, and may use 2 or more types together.
  • the monomer unit constituting the polymer (B) may consist only of the monomer unit (b1) derived from the conjugated diene compound, and the monomer unit (b1) and conjugated diene derived from the conjugated diene compound. It may consist of a monomer unit (b2) derived from a monomer other than the compound. That is, the polymer (B) may be obtained by polymerizing only the conjugated diene compound or may be a copolymer of the conjugated diene compound and a monomer other than the conjugated diene compound.
  • Examples of the monomer unit (b2) derived from a monomer other than the conjugated diene compound include monomer units derived from an aromatic vinyl compound.
  • Examples of the aromatic vinyl compound as the monomer unit (b2) include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, and 4-t-butylstyrene.
  • Aromatic vinyl compounds such as 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene and divinylbenzene Can be mentioned. Of these, styrene, ⁇ -methylstyrene and 4-methylstyrene are preferred.
  • the monomer unit (b2) derived from a monomer other than the conjugated diene the monomer unit (b1) derived from the conjugated diene and the monomer derived from a monomer other than the conjugated diene in the copolymer.
  • the ratio of the monomer unit (b2) derived from the monomer other than the conjugated diene to the total of the monomer units (b2) is a viewpoint of lowering the viscosity of the resin composition, good elongation characteristics and flexibility of the cured product. 1 to 99% by mass is preferable, 1 to 80% by mass is more preferable, 1 to 70% by mass is further preferable, and 1 to 50% by mass is even more preferable.
  • the number average molecular weight (Mn) of the polymer (B) used in the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 180,000, still more preferably 3,000 to 160,000, and 4,000. ⁇ 140,000 is still more preferred, and 5,000 to 120,000 is even more preferred.
  • Mn of the polymer (B) is within the above range, the flexibility and mechanical strength of the cured product are improved, and the resin composition has a low viscosity.
  • the melt viscosity at 38 ° C. of the polymer (B) used in the present invention is preferably 0.1 to 3,000 Pa ⁇ s, more preferably 0.3 to 3,000 Pa ⁇ s, and 0.3 to 2,800 Pa ⁇ s. s is more preferable, 0.5 to 2,600 Pa ⁇ s is still more preferable, and 0.5 to 800 Pa ⁇ s is still more preferable.
  • the melt viscosity of the polymer (B) is within the above range, the resin composition can be uniformly applied to the surface to be coated without unevenness, so that the coating property is improved.
  • the polymer (B) can be obtained by living anion polymerization of a conjugated diene compound and, if necessary, a monomer other than the conjugated diene compound.
  • Living anionic polymerization initiators for living anion polymerization of conjugated diene compounds include, for example, methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium, phenyl lithium, stilbene lithium, etc.
  • Organic monolithium compounds such as dilithiomethane, dilithionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; sodium naphthalene, potassium And naphthalene.
  • compounds such as diisopropenyl benzene and dibenzyl toluene which react with an organic alkali metal compound and give a polyfunctional organic alkali metal compound.
  • the polymer (B) used for this invention may be used individually by 1 type, you may use together 2 or more types of said polymers (B) from which a monomer unit and molecular weight each differ.
  • the mass ratio [(A) / (B)] of the polymer (A) and the polymer (B) is 0.01 to 100, preferably 0.05 to 100, more preferably. It is 0.1 to 50, more preferably 0.1 to 25, and still more preferably 0.1 to 10.
  • the mass ratio [(A) / (B)] is within the above range, a resin composition having a sufficiently low viscosity and a good elongation at break after curing can be obtained.
  • at least one of the polymer (A) and the polymer (B) preferably has a melt viscosity at 38 ° C. of 0.1 to 3,000 Pa ⁇ s, but the polymer (A) and the polymer More preferably, the melt viscosity of both (B) is in the range of 0.1 to 3,000 Pa ⁇ s.
  • the content of the polymerization initiator (C) in the resin composition in the third aspect of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, based on the total amount of the resin composition. 1.0 to 20% by mass is more preferable, 1.0 to 15% by mass is still more preferable, and 1.0 to 10% by mass is most preferable.
  • the content of the polymerization initiator (C) is within the above range, it is preferable in terms of curing speed and mechanical properties.
  • the resin composition in the third aspect of the present invention may contain a monomer (D) as necessary in order to further improve the viscosity, handleability and strength after curing of the resin composition.
  • the monomer (D) preferably has a functional group capable of reacting with the polymer (A).
  • the monomer (D) has a (meth) acryloyl group, an epoxy group, an oxetanyl group, a vinyl ether group, or an alkoxysilyl group in the molecule.
  • the monomer (D) mentioned in the second aspect of the present invention can be preferably used.
  • the monomer (D) includes a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, and a polyfunctional monomer from the viewpoint of good compatibility with the polymer (A). It is preferably at least one selected from functional (meth) acrylates, and more preferably at least one selected from monofunctional (meth) acrylates and bifunctional (meth) acrylates.
  • dicyclopentenyloxyethyl (meth) acrylate dicyclopentanyloxyethyl (meth) acrylate, 1,9-nonanediol di (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like are particularly preferable. These may be used alone or in combination of two or more.
  • the monomer (D) can react with the polymerizable functional group of the polymer (A) with a polymerization initiator such as a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator.
  • the content of the monomer (D) is preferably 0.01 to 1,000 parts by mass, preferably 0.1 to 800 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the polymer (B). Is more preferable, 1.0 to 600 parts by mass is still more preferable, and 1.0 to 400 parts by mass is even more preferable.
  • the content of the monomer (D) is within the above range, the viscosity is lowered and handling properties are improved. Moreover, since the breaking strength and tensile elongation of the cured product are improved when the resin composition in the third aspect of the present invention is cured, a cured product having excellent flexibility can be obtained.
  • the resin composition in the third aspect of the present invention contains a hindered amine compound (E) as necessary in order to further improve the heat resistance and weather resistance of the resin composition and the cured product obtained therefrom. Also good.
  • a hindered amine type compound (E) it is preferable to use the hindered amine type compound which does not have a secondary amino group in a molecule
  • the hindered amine compound (E) having no secondary amino group in the molecule the physical properties of the resin composition and the cured product obtained therefrom are deteriorated and the color tone is changed after being exposed to heat. Can be remarkably improved.
  • the hindered amine compounds (E) mentioned in the second embodiment of the present invention can be suitably used.
  • the content of the hindered amine compound (E) in the resin composition in the third aspect of the present invention is preferably 0.01 to 10% by mass, more preferably 0.5 to 7% by mass, based on the total amount of the resin composition. 1 to 4% by mass is more preferable.
  • the content of the hindered amine compound (E) is within the above range, it is preferable in terms of improving the heat resistance and improving the mechanical properties of the cured product.
  • the resin composition according to the third aspect of the present invention can be polymerized by polymerizing a conjugated diene other than farnesene, in addition to the polymer (A) and the polymer (B), within a range not inhibiting the effects of the present invention.
  • Conjugated dienes other than farnesene include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3- Examples include octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene and chloroprene.
  • the resin composition according to the third aspect of the present invention contains, in addition to the polymer (A) and the polymer (B), a conjugated diene other than farnesene and an aromatic vinyl compound, as long as the effects of the present invention are not impaired.
  • a modified conjugated diene-aromatic vinyl compound copolymer having a polymerizable functional group obtained by copolymerization may be contained. Examples of the conjugated diene are the same as those described above.
  • aromatic vinyl compound examples include styrene, ⁇ -methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-propyl styrene, 4-tert-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl.
  • Styrene 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2-vinyl Naphthalene, vinyl anthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene and the like can be mentioned.
  • Examples of the polymerizable functional group include (meth) acryloyl group, epoxy group, oxetanyl group, vinyl ether group, alkoxysilyl group, (meth) acrylamide group, styrene group, maleimide group, lactone group, lactam group, sulfide group, A thietane group, an acetonide group, a thiourea group, etc. are mentioned.
  • the modified conjugated diene polymer having a polymerizable functional group and the modified conjugated diene-aromatic vinyl compound copolymer having a polymerizable functional group are the polymers according to the fourth embodiment of the present invention described later. It is included in the concept of (F). Therefore, these polymers will be described in detail in the polymer (F) in the fourth embodiment.
  • the contents of the modified conjugated diene polymer and the modified conjugated diene-aromatic vinyl compound copolymer that may be contained in addition to the polymer (A) and the polymer (B) are not particularly limited.
  • the total amount of the resin composition is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 10% by mass or less.
  • the method for producing the resin composition in the third aspect of the present invention is not particularly limited, and for example, the polymer (A), the polymer (B), the polymerization initiator (C), and used as necessary.
  • the other components to be produced can be produced by mixing them at room temperature using ordinary mixing means such as a stirrer or a kneader.
  • the resin composition in the third aspect of the present invention has a melt viscosity at 38 ° C. of preferably 15 Pa ⁇ s or less, more preferably 12 Pa ⁇ s or less, and still more preferably 10 Pa ⁇ s or less.
  • the melt viscosity of the resin composition is within the above range, it is possible to uniformly apply the resin composition to the surface to be coated, and it is easy to prevent air bubbles from being mixed. Become.
  • the melt viscosity of the resin composition is a value determined by the method described in Examples described later.
  • the resin composition according to the third aspect of the present invention has a low melt viscosity, excellent curability, and further provides a cured product excellent in strength, flexibility and transparency.
  • Adhesives can be suitably used.
  • the cured product in the third aspect of the present invention is obtained by curing the resin composition of the present invention in the third aspect.
  • the resin composition in the third aspect of the present invention is irradiated with energy rays.
  • it can be hardened by making the said polymer (A) and a polymerization initiator (C) react by adding heat.
  • energy rays for curing ultraviolet rays are preferable.
  • the ultraviolet light source include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a microwave excimer lamp.
  • an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere in which the oxygen concentration is lowered is preferable.
  • the irradiation atmosphere temperature is preferably 10 to 200 ° C.
  • the UV irradiation amount is preferably 200 to 10,000 mJ / cm 2 .
  • optical pressure sensitive adhesive contains the cured product or resin composition according to the third aspect of the present invention, and is suitable for electronic devices such as smartphones, liquid crystal displays, and organic EL displays. Can be used.
  • additives can be appropriately added as necessary without departing from the object of the present invention.
  • the additive include a tackifier, a plasticizer, a pigment, a colorant, an anti-aging agent, and an ultraviolet absorber.
  • the resin composition according to the fourth aspect of the present invention is the monomer unit (f1) derived from a conjugated diene compound having 12 or less carbon atoms in the resin composition according to the second aspect or the third aspect of the present invention. And a polymer (F) having a polymerizable functional group, and the mass ratio [(A) / (F)] of the polymer (A) to the polymer (F) is 0.01 to 100 It is a resin composition.
  • the polymer (F) used for the resin composition in the fourth aspect of the present invention is a polymer having a polymerizable functional group containing a monomer unit (f1) derived from a conjugated diene compound having 12 or less carbon atoms.
  • Conjugated diene compounds having 12 or less carbon atoms as monomer units (f1) are butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene.
  • 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, chloroprene and the like are preferable.
  • the monomer unit constituting the polymer (F) may be composed only of the monomer unit (f1) derived from the conjugated diene compound having 12 or less carbon atoms, and the monomer unit derived from the conjugated diene compound ( f1) and a monomer unit (f2) derived from a monomer other than the conjugated diene compound having 12 or less carbon atoms (excluding farnesene). That is, the polymer (F) may be obtained by polymerizing only the conjugated diene compound having 12 or less carbon atoms, and a monomer other than the conjugated diene compound having 12 or less carbon atoms and the conjugated diene compound having 12 or less carbon atoms. And a copolymer thereof.
  • Examples of the monomer as the monomer unit (f2) include aromatic vinyl compounds.
  • Examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2- Vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlor
  • a monomer unit (f2) derived from a monomer other than a conjugated diene having 12 or less carbon atoms a monomer unit (f1) derived from a conjugated diene compound having 12 or less carbon atoms in the copolymer, And the ratio of the monomer unit (f2) derived from the monomer other than the conjugated diene having 12 or less carbon atoms to the total of the monomer units (f2) derived from the monomer other than the conjugated diene having 12 or less carbon atoms Is preferably 1 to 99% by mass, more preferably 1 to 80% by mass, and more preferably 1 to 70% by mass from the viewpoint of reducing the viscosity of the resin composition and maintaining good elongation characteristics and flexibility of the cured product. More preferred is 1 to 50% by mass.
  • the same functional groups as those exemplified as the polymerizable functional group possessed by the polymer (A) can be used.
  • These functional groups may have a substituent.
  • the number average molecular weight (Mn) of the polymer (F) used in the present invention is preferably 1,000 to 200,000, more preferably 5,000 to 200,000, still more preferably 8,000 to 100,000, and 11,000. Even more preferred is ⁇ 60,000.
  • Mn of the polymer (F) is within the above range, the flexibility and mechanical strength of the cured product are improved and the resin composition has a low viscosity.
  • the melt viscosity at 38 ° C. of the polymer (F) used in the present invention is preferably 0.1 to 3,000 Pa ⁇ s, more preferably 0.3 to 3,000 Pa ⁇ s, and more preferably 0.3 to 2,800 Pa ⁇ s. s is more preferable, 0.5 to 2,600 Pa ⁇ s is still more preferable, and 0.5 to 800 Pa ⁇ s is still more preferable.
  • the melt viscosity of the polymer (F) is within the above range, the resin composition can be uniformly applied to the surface to be coated, so that the coating property is improved.
  • the said polymer (F) can be manufactured by the method similar to the said polymer (A). Specifically, a functional group that can be polymerized by first polymerizing a conjugated diene compound having 12 or less carbon atoms and, if necessary, a monomer other than the conjugated diene compound having 12 or less carbon atoms by an emulsion polymerization method or a solution polymerization method. An unmodified polymer having no groups is produced. Subsequently, it can obtain by introduce
  • the polymer (F) may be a commercially available product.
  • the total content of the polymer (A) and the polymer (F) in the resin composition is preferably 1 to 99% by mass, more preferably 2 to 98% by mass, still more preferably 5 to 95% by mass. 90% by mass is even more preferable, and 15 to 85% by mass is even more preferable.
  • a cured product excellent in strength, flexibility, low moisture permeability and transparency can be provided.
  • the mass ratio [(A) / (F)] of the polymer (A) and the polymer (F) is 0.01 to 100, preferably 0.05 to 100, more preferably. It is 0.1 to 50, more preferably 0.1 to 25, and still more preferably 0.1 to 10.
  • the mass ratio [(A) / (F)] is within the above range, a resin composition having a sufficiently low viscosity and a good elongation at break after curing can be obtained.
  • Example of the first aspect of the present invention Each component used in the example and comparative example of the first aspect is as follows. ⁇ Polymer (A) having polymerizable functional group> -Polyfarnesene (A-1) to (A-5) having a methacryloyl group in the molecule obtained in Production Examples 1 to 5 described later
  • ⁇ Radical polymerization initiator> 2-hydroxy-2-methyl-1-phenylpropan-1-one manufactured by BASF Corporation, trade name “DAROCUR 1173”
  • ⁇ Anti-aging agent> ⁇ 2,6-Di-t-butyl-4-methylphenol (BHT) Made by Honshu Chemical Industry Co., Ltd.
  • Production Example 1 Polyfarnesene (A-1) having a methacryloyl group in the molecule Charge 1520 g of cyclohexane and 7.8 g of 10.5 wt% cyclohexane solution of sec-butyllithium into a 5 liter autoclave that has been purged with nitrogen, then warm to 50 ° C and add 1510 g of ⁇ -farnesene Then, polymerization was performed for 2 hours. The obtained polymerization solution was poured into methanol to reprecipitate the unmodified polymer, and was filtered off, followed by vacuum drying at 80 ° C.
  • Polymer (A-1) Polymer (A-1) ” may be obtained.
  • Production Examples 2 and 3 Polyfarnesene having a methacryloyl group in the molecule (A-2), (A-3) An unmodified polymer was produced in the same manner as in Production Example 1, except that the amounts of ⁇ -farnesene, sec-butyllithium, and cyclohexane were changed to the amounts shown in Table 1, respectively.
  • Table 1 shows the number average molecular weight and molecular weight distribution of the unmodified polymer.
  • polyfarnesene (A-2) and (A-3) each having a methacryloyl group in the molecule was produced by reacting each unmodified polymer in the same manner as in Example 1 (hereinafter, methacryloyl group was added in the molecule).
  • polyfarnesene (A-2) having a methacryloyl group in the molecule may be referred to as “polymer (A-2)”.
  • the obtained polymerization solution was poured into methanol, the unmodified polymer was reprecipitated and filtered, and vacuum dried at 80 ° C. for 10 hours to obtain 1200 g of farnesene-isoprene copolymer (unmodified polymer). It was.
  • the number average molecular weight (Mn) of standard polystyrene conversion was 25,300, and the molecular weight distribution (Mw / Mn) was 1.09.
  • 300 g of the unmodified polymer obtained in a 1 liter autoclave subjected to nitrogen substitution was charged, 4.5 g of maleic anhydride and 3.0 g of BHT were added, and reacted at 160 ° C.
  • Production Example 5 Farnesene-isoprene copolymer having a methacryloyl group in the molecule (A-5) An unmodified polymer was produced in the same manner as in Production Example 4 except that the amounts of ⁇ -farnesene, sec-butyllithium and cyclohexane were changed to the amounts shown in Table 1, respectively. Table 1 shows the number average molecular weight and molecular weight distribution of the unmodified polymer. Next, the unmodified polymer is reacted in the same manner as in Example 4 to obtain a farnesene-isoprene copolymer having a methacryloyl group in the molecule (hereinafter sometimes referred to as “polymer (A-5)”). Manufactured.
  • Comparative Production Example 1 Polyisoprene having a methacryloyl group in the molecule (IX-1) Into an autoclave having a capacity of 5 liters subjected to nitrogen substitution, 1420 g of cyclohexane and 70.9 g of a 10.5 mass% cyclohexane solution of sec-butyllithium were charged, the temperature was raised to 50 ° C., and 1490 g of isoprene was added, Polymerization was performed for 2 hours. The obtained polymerization solution was poured into methanol to reprecipitate polyisoprene, followed by filtration, and vacuum drying at 80 ° C. for 10 hours to obtain 1200 g of polyisoprene.
  • Example 1 For the polymer (A-1), the number average molecular weight, methacryloyl equivalent, number of functional groups per molecular chain and melt viscosity were measured by the methods described later. The results are shown in Table 2. Further, 3 parts by mass of a radical polymerization initiator was added to 100 parts by mass of the polymer (A-1) to prepare a curable resin composition. With respect to the obtained curable resin composition, the curing rate, transparency, curing shrinkage rate, breaking strength, breaking elongation, moisture permeability and hardness were evaluated by the methods described later. The results are shown in Table 2.
  • Example 2-5 Various evaluations were performed in the same manner as in Example 1 except that the polymer (A-1) was changed to the polymers (A-2) to (A-5). The results are shown in Table 2.
  • GPC device GPC device “GPC8020” manufactured by Tosoh Corporation Separation column: “TSKgel G4000HXL” manufactured by Tosoh Corporation ⁇ Detector: “RI-8020” manufactured by Tosoh Corporation ⁇ Eluent: Tetrahydrofuran ⁇ Eluent flow rate: 1.0 ml / min ⁇ Sample concentration: 5 mg / 10 ml -Column temperature: 40 ° C
  • UV irradiation device manufactured by GS Yuasa Corporation, using HAK125L-F as a mercury lamp
  • setting illuminance 30mW / cm 2 and conveyor speed 2m / min. was irradiated with 150 mJ / cm 2 of UV. This was repeated 1, 2, 4, 6, 8, and 16 times to obtain 500 mg of cured products having a total UV irradiation amount of 150, 300, 600, 900, 1200, and 2400 mJ / cm 2 , respectively.
  • the cured product was immersed in toluene at room temperature for 24 hours, the insoluble part was filtered off with a 200 mesh wire net, washed, and then vacuum dried at 80 ° C. for 12 hours. After drying, each sample was weighed, and the polymer gel fraction at each UV irradiation dose was calculated according to the following formula.
  • (I-6) Curing Shrinkage Ratio The density of the cured product obtained in the above (I-5) was measured based on the method described in JIS K 6911, and this was used as the density of the composition after curing. The density of the composition before curing was measured using a specific gravity bottle method described in JIS K0061. After measuring the density before and after curing, the curing shrinkage was determined based on the following formula and evaluated according to the following criteria.
  • Curing shrinkage (%) [1 ⁇ (density of composition before curing) / (density of composition after curing)] ⁇ 100 ⁇ Evaluation criteria> 5: Curing shrinkage rate is less than 1% 4: Curing shrinkage rate is 1% or more and less than 3% 3: Curing shrinkage rate is 3% or more and less than 5% 2: Curing shrinkage rate is 5% or more and less than 10% 1: Curing shrinkage is 10% or more
  • Moisture permeability is less than 25 g / m 2 ⁇ 24 h 4: Moisture permeability is 25 g / m 2 ⁇ 24 h or more, less than 50 g / m 2 ⁇ 24 h 3: Moisture permeability is 50 g / m 2 ⁇ 24 h or more, 100 g / m 2 ⁇ Less than 24 h 2: Moisture permeability is 100 g / m 2 ⁇ 24 h or more, less than 200 g / m 2 ⁇ 24 h 1: Moisture permeability is 200 g / m 2 ⁇ 24 h or more
  • the polymers (A-3) to (A-5) of the present invention have a lower melt viscosity at the same molecular weight than the polyisoprene (IX-1). Further, the polymers (A-1) to (A-5) of the present invention have a faster curing rate than the polyisoprene (IX-1), and in particular, polymers having a high molecular weight as in Examples 1 and 2. (A-1) and (A-2) are excellent in curing rate. Further, the polymers (A-1) to (A-5) of the present invention have good transparency, low curing shrinkage, low moisture permeability, and flexibility, like the polyisoprene (IX-1). You can see that it has.
  • the curable resin (IX-2) of Comparative Example 2 gels in the process of producing a polyfarnesene 2-hydroxyethyl methacrylate modified product and becomes insoluble in a solvent, so the number average molecular weight and methacryloyl equivalent are measured. I could't.
  • Comparative Example 3 using urethane acrylate (IX-3) is excellent in the curing rate as in Examples 1 to 5, but the polymer (A--) of the present invention is excellent in terms of shrinkage ratio and moisture permeability during curing. 1) to (A-5) were superior.
  • Example of the second aspect of the present invention Each component used in the Example of the 2nd mode and a comparative example is as follows.
  • Polymer (A) having polymerizable functional group Polymers (A-1) to (A-5) used in Examples 1 to 5 of the first aspect Table 3 shows the number average molecular weight, molecular weight distribution, melt viscosity, methacryloyl equivalent and the number of polymerizable functional groups per molecular chain of the polymers (A-1) to (A-5).
  • Hindered amine compounds (E-1) A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, manufactured by BASF Corporation, trade name "TINUVIN 765"
  • ⁇ Anti-aging agent > ⁇ 2,6-Di-tert-butyl-4-methylphenol (BHT) manufactured by Honshu Chemical Industry Co., Ltd.
  • TEA-1000 2-hydroxyethyl methacrylate
  • Table 5 shows polymers (A-1) to (A-5), monomers (D-1) to (D-3), a polymerization initiator (C-1), and a hindered amine compound (E-1).
  • a resin composition was prepared and evaluated in the same manner as in Example 6 except that it was blended in the ratio shown. The results are shown in Table 5.
  • Moisture permeability test The cured product obtained in (II-5) above was tested in the same manner as (I-8) in the first embodiment, and evaluated according to the following criteria.
  • Examples 6 to 10 use polymers (A-1) to (A-5) containing monomer units derived from farnesene, and polymers containing no monomers derived from farnesene (II-X— Compared to Comparative Example 8 using 5), the viscosity is low and the curability is excellent, and the obtained cured product has a high elongation at break and low hardness, and is excellent in flexibility. Further, the resin compositions according to Examples 11 to 14 using the polymer (A-3) have a lower viscosity than that of Comparative Example 8, but the curing rate is equal to or higher than that.
  • Examples 6 to 14 are superior in curing shrinkage and moisture permeability compared to Comparative Example 4 in which urethane acrylate (II-X-1) is used instead of the polymer containing the farnesene monomer.
  • the polymer (II-X-2) used in Comparative Example 5 gelled in the course of producing the polyfarnesene-modified 2-hydroxyethyl methacrylate, and a uniform polymer could not be obtained. As a result, the number average molecular weight and methacryloyl equivalent could not be measured. Moreover, evaluation as another resin composition could not be performed.
  • Example of the third aspect of the present invention The components used in the examples and comparative examples of the third aspect are as follows. ⁇ Polymer (A) having polymerizable functional group> -Polymers (A-1), (A-3) and (A-5) used in Examples 1, 3 and 5 of the first aspect
  • Hindered amine compounds (E-1) A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, manufactured by BASF Corporation, trade name "TINUVIN 765"
  • Production Example 6 Liquid polybutadiene (B-1) By subjecting butadiene to anionic polymerization in n-hexane using n-butyllithium as an initiator, a liquid polybutadiene having a number average molecular weight of 9,000 (hereinafter also referred to as “polymer (B-1)”) was synthesized. Table 7 shows the physical properties of the polymer (B-1).
  • Production Example 7 Liquid polyisoprene (B-2) Isoprene was anionically polymerized in n-hexane using n-butyllithium as an initiator to obtain liquid polyisoprene having a number average molecular weight of 9,000. (Hereinafter also referred to as “polymer (B-2)”) was synthesized. Table 7 shows the physical properties of the polymer (B-2).
  • Production Example 8 Liquid polyisoprene (B-3) Liquid polyisoprene having a number average molecular weight of 20,000 (hereinafter also referred to as “polymer (B-3)”) was synthesized by anionic polymerization of isoprene in n-hexane using n-butyllithium as an initiator. . Table 7 shows the physical properties of the polymer (B-3).
  • the evaluation method in the Example of the third aspect is as follows.
  • (III-1) Measurement of number average molecular weight and molecular weight distribution
  • the number average molecular weight and molecular weight distribution were measured by the same method as in (I-1) of the first embodiment.
  • Table 7 the first decimal place is rounded off to the nearest whole number.
  • Example 24 When Examples 24, 25, 26, 29, and 30 were compared with Example 2 of Example 6, Example 27 and Example 8 of Example 2, and Example 28 and Example 10 of Example 2 were compared, respectively, (A) A resin composition containing a modified liquid polyfarnesene having a methacryloyl group which is a functional group polymerizable in the molecule as a component, and a liquid diene rubber as a component (B) has an appearance and breaking elongation by active energy ray curing. It turns out that the hardened
  • Example of the fourth aspect of the present invention The components used in the examples and comparative examples of the fourth aspect are as follows. ⁇ Polymer (A) having polymerizable functional group> -Polymers (A-1) and (A-3) used in Examples 1 and 3 of the first aspect
  • Hindered amine compounds (E-1) A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, manufactured by BASF Corporation, trade name "TINUVIN 765"
  • the evaluation method in the Example of the fourth aspect is as follows.
  • (IV-1) Melt Viscosity
  • the resin compositions obtained in the examples were measured by the same method as (I-3) in the first aspect.
  • Example 35 and the first aspect Example 3, Example 36 and the second aspect Example 8, Example 37 and the third aspect Example 27, and Example 38 and the third aspect Example 31 are respectively compared. It can be seen that the composition obtained by mixing the polymer (F) in addition to the polymer (A) also gives a cured product comparable to other embodiments by active energy ray curing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un polymère qui a un groupe fonctionnel polymérisable et contient une unité monomère (a1) issue de Farnesène comme monomère à l'aide d'une configuration du polymère. Cette composition de résine contient le polymère (A) ayant un groupe fonctionnel polymérisable et contenant une unité monomère (a1) issue de Farnesène comme unité monomère configurant le polymère.
PCT/JP2014/059135 2013-03-29 2014-03-28 Polymère, son procédé de production et composition de résine contenant ledit polymère WO2014157624A1 (fr)

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JP2019532142A (ja) * 2016-09-15 2019-11-07 フィナ テクノロジー，インコーポレイティド ファルネセン系マクロモノマー並びにその製造及び使用方法
JP7185645B2 (ja) 2017-06-07 2022-12-07 フィナ テクノロジー，インコーポレイティド シラン官能化ポリ（ファルネセン）及びそれを含むゴムコンパウンド
JP2020523441A (ja) * 2017-06-07 2020-08-06 フィナ テクノロジー，インコーポレイティド シラン官能化ポリ（ファルネセン）及びそれを含むゴムコンパウンド
JP2020531631A (ja) * 2017-08-18 2020-11-05 フィナ テクノロジー，インコーポレイティド エポキシ化ポリファルネセン及びその製造方法
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JP7189936B2 (ja) 2017-08-18 2022-12-14 フィナ テクノロジー，インコーポレイティド エポキシ化ポリファルネセン及びその製造方法
US20190055336A1 (en) * 2017-08-18 2019-02-21 Fina Technology, Inc. Epoxidized polyfarnesene and methods for producing the same
WO2019036636A1 (fr) * 2017-08-18 2019-02-21 Fina Technology, Inc. Polyfarnésène époxydé et procédés de production de ce dernier
JP2020041101A (ja) * 2018-09-13 2020-03-19 ダイセル・オルネクス株式会社 ウレタン（メタ）アクリレート、これを含む活性エネルギー線硬化性組成物、及びその硬化物
WO2020054582A1 (fr) * 2018-09-13 2020-03-19 ダイセル・オルネクス株式会社 (méth)acrylate d'uréthane, composition durcissable par rayonnement d'énergie active le contenant, et produit durci de ladite composition
JP7213042B2 (ja) 2018-09-13 2023-01-26 ダイセル・オルネクス株式会社 ウレタン（メタ）アクリレート、これを含む活性エネルギー線硬化性組成物、及びその硬化物
WO2020212492A1 (fr) 2019-04-16 2020-10-22 University Of Durham Procédé d'époxydation
US11466118B2 (en) 2019-11-22 2022-10-11 Fina Technology, Inc. Chain end hydroxyl functionalized branched polyfarnesenes obtained by radical polymerization

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KR20150135305A (ko) 2015-12-02
KR102167198B1 (ko) 2020-10-20

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