WO2017217363A1 - Composition de résine pour moulage, et article moulé - Google Patents

Composition de résine pour moulage, et article moulé Download PDF

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Publication number
WO2017217363A1
WO2017217363A1 PCT/JP2017/021640 JP2017021640W WO2017217363A1 WO 2017217363 A1 WO2017217363 A1 WO 2017217363A1 JP 2017021640 W JP2017021640 W JP 2017021640W WO 2017217363 A1 WO2017217363 A1 WO 2017217363A1
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meth
polymer block
acrylate
group
block copolymer
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PCT/JP2017/021640
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English (en)
Japanese (ja)
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河合　道弘
成志 山田
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東亞合成株式会社
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Priority to JP2018523891A priority Critical patent/JP6835088B2/ja
Publication of WO2017217363A1 publication Critical patent/WO2017217363A1/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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a molding resin composition and a molded product using the same.
  • the resin composition for molding of the present invention contains a block polymer having a specific structure.
  • Patent Documents 1 and 2 propose the use of a reactive molding resin using a two-component epoxy resin.
  • these have problems such as complicated handling due to the two-component type, limited pot life and a curing period for the curing reaction.
  • curing arises, there also existed a problem that damage of a device produced depending on the case.
  • Patent Document 3 the melt viscosity at 200 ° C. is 5 to 1,000 dPa ⁇ s or less, the tensile strength at break of the film-shaped molded product is a (N / mm 2), and the tensile elongation at break is b (%). ), A saturated polyester resin for molding having a product a ⁇ b of 500 or more is disclosed.
  • Patent Document 4 discloses a specific low-pressure molding thermoplastic resin composition comprising a polyalphaolefin, a tackifier resin, and an antioxidant.
  • Patent Document 5 discloses an overmold composition containing a specific acrylic block copolymer and a tackifier.
  • the polyester resin described in Patent Document 3 is excellent in electrical insulation and water resistance, but has insufficient heat resistance.
  • the resin when exposed to a high temperature of about 150 ° C. for a long time, the resin is oxidized. The mechanical strength may be reduced due to deterioration.
  • the olefin-based resin composition described in Patent Document 4 also has insufficient heat resistance, and it has been difficult to apply it to the current use environment of electronic components.
  • fuel resistance required for automobile applications That is, since it swells with gasoline, the durability is not sufficient.
  • the acrylic block copolymer described in Patent Document 5 is also not satisfactory in terms of heat resistance and fuel resistance. Thus, no hot-melt type molding composition that can be applied to an electronic device having a complicated shape has yet been presented with sufficient heat resistance and oil resistance.
  • the present invention has been made in view of the above circumstances, and an object thereof is a thermoplastic resin composition excellent in moldability that can be used as a hot melt mold, and a molding composition excellent in heat resistance and oil resistance. It is a problem to provide.
  • the other subject of this invention is providing the molded article obtained using the said molding composition.
  • thermoplastic block copolymer having a polymer block containing a structural unit derived from a specific monomer as a hard segment.
  • the inventors have found that the above various performances are excellent, and have completed the present invention.
  • the polymer block (A) has a glass transition temperature (hereinafter referred to as “Tg”) of 50 ° C. or higher and is selected from the group consisting of an amide group-containing vinyl compound, a maleimide compound, and an aromatic monomer. Having structural units derived from at least one radical polymerizable monomer,
  • the polymer block (B) includes a structural unit having a Tg of ⁇ 10 ° C. or less and derived from a (meth) acrylic acid ester compound. Molding resin composition.
  • the molding resin composition of the present invention can be used as hot melt molding, it can be applied to electric and electronic parts having complicated shapes. Moreover, according to the said molding resin composition, the molded object which exhibits extremely high heat resistance and oil resistance can be obtained.
  • (meth) acryl means acryl and methacryl
  • (meth) acrylate means acrylate and methacrylate
  • the “(meth) acryloyl group” means an acryloyl group and a methacryloyl group.
  • the block copolymer contained in the molding composition of the present invention includes a polymer block (A) corresponding to a hard segment and a polymer block (B) corresponding to a soft segment. ) Each.
  • the present block copolymer has two or more polymer blocks (A) and / or polymer blocks (B), the structures of the blocks may be the same or different.
  • the polymer block (A) forms a hard segment and is at least one radical polymerization selected from the group consisting of an amide group-containing vinyl compound, a maleimide compound and an aromatic monomer. Having a structural unit derived from a functional monomer. When a polymer block (A) has said structural unit, it can be set as the molding composition excellent in heat resistance and oil resistance.
  • the amide group-containing vinyl compound examples include (meth) acrylamide, methyl (meth) acrylamide, ethyl (meth) acrylamide, n-propyl (meth) acrylamide, isopropyl (meth) acrylamide, and n-butyl (meth) N-monoalkyl substituted (meth) such as) acrylamide, isobutyl (meth) acrylamide, tert-butyl (meth) acrylamide, n-hexyl (meth) acrylamide, n-octyl (meth) acrylamide and 2-ethylhexyl (meth) acrylamide Acrylamide compounds; N-dialkyl-substituted (meth) acrylamide compounds such as dimethyl (meth) acrylamide, diethyl (meth) acrylamide and dibutyl (meth) acrylamide; N-methylaminoethyl (meth) acrylate N-
  • a structural unit derived from the amide group-containing vinyl compound By polymerizing the amide group-containing vinyl compound, a structural unit derived from the amide group-containing vinyl compound can be introduced into the polymer block (A).
  • the amide group-containing vinyl compound an N-dialkyl-substituted (meth) acrylamide compound in which the total number of carbon atoms of the substituted alkyl group is 2 to 8 or a (meth) acrylamide derivative having a cyclic structure is used from the viewpoint of heat resistance and oil resistance.
  • dimethyl (meth) acrylamide, diethyl (meth) acrylamide and (meth) acryloylmorpholine may be used.
  • the maleimide compounds include maleimide and N-substituted maleimide compounds.
  • Specific examples of the N-substituted maleimide compound include, for example, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-tert N-alkyl substituted maleimide compounds such as -butylmaleimide, N-pentylmaleimide, N-hexylmaleimide, N-heptylmaleimide, N-octylmaleimide, N-laurylmaleimide and N-stearylmaleimide; N-cyclopentylmaleimide and N-cyclohexyl N-cycloalkyl substituted maleimide compounds such as maleimide; N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-acet
  • a structural unit derived from the maleimide compound can be introduced into the polymer block (A).
  • a compound represented by the following general formula (1) may be used.
  • R 1 is hydrogen, an alkyl group having 1 to 3 carbon atoms, or PhR 2 .
  • Ph is a phenyl group.
  • R 2 is hydrogen, a hydroxy group, an alkoxy group having 1 to 2 carbon atoms, an acetyl group, or a halogen.
  • the aromatic monomer includes styrene and its derivatives. Specific compounds include styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, vinyl toluene, vinyl xylene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o-ethyl styrene, m-ethyl.
  • a structural unit derived from the aromatic monomer By polymerizing the aromatic monomer, a structural unit derived from the aromatic monomer can be introduced into the polymer block (A).
  • aromatic monomers for example, from the viewpoint of polymerizability, for example, styrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, and p. -Hydroxystyrene may be used.
  • the proportion of structural units derived from at least one radical polymerizable monomer selected from the group consisting of amide group-containing vinyl compounds, maleimide compounds and aromatic monomers is heavy. It can be 30% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more with respect to the total structural unit of the combined block (A).
  • the upper limit is 100% by mass, may be 99% by mass or less, may be 95% by mass or less, and may be 90% by mass or less.
  • the range of the structural unit derived from at least one radical polymerizable monomer selected from the group consisting of an amide group-containing vinyl compound, a maleimide compound and an aromatic monomer is, for example, 30% by mass or more and 100% by mass or less.
  • a structural unit derived from at least one radical polymerizable monomer selected from the group consisting of an amide group-containing vinyl compound, a maleimide compound, and an aromatic monomer is based on all structural units of the polymer block (A). When it is 30% by mass or more, the heat resistance and oil resistance of the molded product obtained from the present block copolymer and the molding resin composition containing the block copolymer are improved.
  • the polymer block (A) may contain a crosslinkable functional group.
  • a crosslinkable functional group By cross-linking the block copolymer using the cross-linkable functional group, a molded article having excellent mechanical properties can be obtained from the molding composition containing the block copolymer.
  • the crosslinkable functional group may be introduced by using, for example, a styrene derivative and / or a maleimide compound having a functional group such as a hydroxy group or by copolymerizing a vinyl compound having a crosslinkable functional group. Can do.
  • vinyl compounds having a crosslinkable functional group include unsaturated carboxylic acids, unsaturated acid anhydrides, hydroxy group-containing vinyl compounds, epoxy group-containing vinyl compounds, primary or secondary amino group-containing vinyl compounds, and reactive silicon groups. Examples thereof include compounds. These compounds may be used alone or in combination of two or more.
  • unsaturated carboxylic acids include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, cinnamic acid, and monoalkyl esters of unsaturated dicarboxylic acids (maleic acid, fumaric acid). Acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride, monoalkyl esters such as citraconic anhydride) and the like. These compounds may be used alone or in combination of two or more.
  • unsaturated acid anhydride examples include maleic anhydride, itaconic anhydride and citraconic anhydride. These compounds may be used alone or in combination of two or more.
  • hydroxy group-containing vinyl compound examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
  • epoxy group-containing vinyl compound examples include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.
  • the primary or secondary amino group-containing vinyl compound examples include aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, and the like.
  • Amino group-containing (meth) acrylic acid esters amino group-containing (amino) (meth) acrylamide, aminopropyl (meth) acrylamide, N-methylaminoethyl (meth) acrylamide, N-ethylaminoethyl (meth) acrylamide and the like
  • And (meth) acrylamide these compounds may be used alone or in combination of two or more.
  • the reactive silicon group-containing compound examples include vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane and vinyldimethylmethoxysilane; (meth) acrylic acid trimethoxysilylpropyl, (meth) Silyl group-containing (meth) acrylate esters such as triethoxysilylpropyl acrylate, methyldimethoxysilylpropyl (meth) acrylate and dimethylmethoxysilylpropyl (meth) acrylate; silyl group-containing vinyl ethers such as trimethoxysilylpropyl vinyl ether And silyl group-containing vinyl esters such as vinyl trimethoxysilylundecanoate. These compounds may be used alone or in combination of two or more.
  • an oxazoline group or an isocyanate group can be introduced as a crosslinkable functional group by copolymerizing an oxazoline group-containing monomer or an isocyanate group-containing monomer.
  • the polyfunctional polymerizable monomer is a compound having two or more polymerizable functional groups such as a (meth) acryloyl group and an alkenyl group in the molecule, a polyfunctional (meth) acrylate compound, a polyfunctional alkenyl compound, And compounds having both a (meth) acryloyl group and an alkenyl group.
  • allyl (meth) acrylate isopropenyl (meth) acrylate, butenyl (meth) acrylate, pentenyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, etc.
  • a compound having both a (meth) acryloyl group and an alkenyl group in the molecule there is a difference in the reactivity of the polymerizable unsaturated group, so that the polymer block (A) is effectively polymerizable unsaturated.
  • a group can be introduced.
  • These compounds may be used alone or in combination of two or more.
  • the amount of the crosslinkable functional group introduced is preferably 0.01 mol% or more based on the total structural units of the polymer block (A). It may be 0.1 mol% or more, 1.0 mol% or more, or 2.0 mol% or more. When the amount of the crosslinkable functional group introduced is 0.01 mol% or more, an effect can be recognized in improving the mechanical properties.
  • the upper limit of the cross-linkable functional group introduction amount can be 60 mol%, 40 mol% or less, 20 mol% or less, or 10 mol%. It may be less than mol%.
  • the amount of the crosslinkable functional group introduced can be, for example, in the range of 0.01 to 60 mol%, and in the range of 0.1 to 40 mol%, based on the total structural units of the polymer block (A). It may be in the range of 1.0 to 20 mol%.
  • the polymer block (A) may have a structural unit derived from another monomer copolymerizable with these, in addition to the monomer unit, as long as the effects of the present invention are not impaired.
  • examples of other monomers include (meth) acrylic acid alkyl ester compounds and (meth) acrylic acid alkoxyalkyl ester compounds. These compounds may be used alone or in combination of two or more.
  • the proportion of the structural units derived from the other monomers described above is, for example, in the range of 0 to 50% by mass with respect to the total structural units of the polymer block (A). It may be 5 to 45% by mass or 10 to 40% by mass.
  • (meth) acrylic acid alkyl ester compound examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid n.
  • the (meth) acrylic acid alkoxyalkyl ester compound examples include methoxymethyl (meth) acrylate, ethoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) N-propoxyethyl acrylate, n-butoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, n-propoxypropyl (meth) acrylate, n- (meth) acrylate
  • Examples include butoxypropyl, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, n-propoxybutyl (meth) acrylate, and n-butoxybutyl (meth) acrylate.
  • monomers other than the above include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like.
  • Tg of the polymer which comprises a polymer block (A) is 50 degreeC or more.
  • Tg may be 100 ° C. or higher, 120 ° C. or higher, 150 ° C. or higher, 180 ° C. or higher, or 200 ° C. or higher.
  • the upper limit of Tg is 350 ° C. or less due to the limitation of the constituent monomer units that can be used.
  • the upper limit of Tg may be 300 ° C. or lower, 280 ° C. or lower, or 250 ° C. or lower.
  • the value of Tg can be obtained by differential scanning calorimetry as described in Examples described later. Moreover, it can also obtain
  • the solubility parameter (hereinafter referred to as “SP value”) of the polymer block (A) can be 10.0 or more. If the SP value is 10.0 or more, the oil resistance of the present block copolymer may be better.
  • the SP value may be 11.0 or more, or 12.0 or more.
  • the upper limit of the SP value of the polymer block (A) is not particularly limited, but is usually 30 or less.
  • the polymer block (B) forms a soft segment and has a structural unit derived from a (meth) acrylic acid ester compound.
  • a molding composition having excellent mechanical properties and moldability can be obtained.
  • the (meth) acrylate compound examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate.
  • a (meth) acrylic acid ester compound having a functional group such as an amide group, an amino group, a carboxy group, or a hydroxy group may be used.
  • the acrylic monomer is a (meth) acrylic acid alkyl ester compound having an alkyl group having 1 to 3 carbon atoms or an alkoxyalkyl group having 2 to 3 carbon atoms. May be included.
  • the proportion of the structural units derived from the (meth) acrylic acid ester compound can be 10% by mass or more based on the total structural units of the polymer block (B), and 20% by mass. % Or more, 50 mass% or more, 70 mass% or more, 80 mass% or more, or 90 mass% or more.
  • the upper limit of the structural unit derived from the (meth) acrylic acid ester compound is 100% by mass or less, may be 99% by mass or less, or may be 95% by mass or less.
  • the range occupied by the structural unit derived from the (meth) acrylic acid ester compound can be, for example, 10% by mass or more and 100% by mass or less, and may be 20% by mass or more and 100% by mass or less, and 50% by mass or more.
  • the polymer block (B) can use monomers other than the (meth) acrylic acid ester compound as constituent monomer units.
  • monomers other than the (meth) acrylic acid ester compound (meth) acrylic acid, (meth) acrylamide and derivatives thereof, and a monomer having an unsaturated group other than the (meth) acryloyl group may be used. it can. Examples thereof include alkyl vinyl esters, alkyl vinyl ethers, and aliphatic or aromatic vinyl compounds such as styrene and styrene derivatives.
  • the Tg of the polymer constituting the polymer block (B) in this block copolymer is ⁇ 10 ° C. or lower.
  • Tg may be ⁇ 20 ° C. or lower, ⁇ 30 ° C. or lower, or ⁇ 40 ° C. or lower.
  • the lower limit of Tg is ⁇ 80 ° C. due to the limitation of constituent monomer units that can be used.
  • Tg is ⁇ 20 ° C. or lower, it is preferable in terms of ensuring flexibility even in a low temperature environment. In consideration of cold resistance, it is more preferably ⁇ 30 ° C. or less, and further preferably ⁇ 40 ° C. or less.
  • the SP value of the polymer block (B) can be 9.9 or more.
  • the oil resistance of the present block copolymer may be better.
  • the SP value may be 10.0 or more, or 10.1 or more.
  • the upper limit of the SP value of the polymer block (B) is not particularly limited, but is usually 20 or less.
  • the polymer block (B) may contain a crosslinkable functional group, and the oil resistance of the molded object obtained from a molding resin composition can be improved.
  • the crosslinkable functional group can be introduced, for example, by copolymerizing a vinyl compound having a crosslinkable functional group.
  • vinyl compounds having a crosslinkable functional group include unsaturated carboxylic acids, unsaturated acid anhydrides, hydroxy group-containing vinyl compounds, epoxy group-containing vinyl compounds, primary or secondary amino group-containing vinyl compounds, and reactive silicon groups. Examples thereof include compounds. These compounds may be used alone or in combination of two or more.
  • the amount of the crosslinkable functional group introduced can be 0.01 mol% or more based on the total structural unit of the polymer block (B), 0.1 mol% or more may be sufficient and 0.5 mol% or more may be sufficient. If the amount of the crosslinkable functional group introduced is 0.01 mol% or more, the oil resistance of the molded product obtained from the molding resin composition may be improved. On the other hand, from the viewpoint of moldability, the upper limit of the amount of the crosslinkable functional group introduced can be 20 mol% or less, may be 10 mol% or less, and may be 5 mol% or less.
  • the amount of the crosslinkable functional group introduced can be, for example, in the range of 0.01 to 20 mol% based on the total structural units of the polymer block (B), and in the range of 0.1 to 10 mol%. It may be in the range of 0.5 to 5 mol%.
  • the block copolymer of the present invention has one or more of the polymer block (A) and the polymer block (B).
  • the structure of each block may be the same or different.
  • A- (BA) n type such as ABA triblock copolymer comprising polymer block (A) -polymer block (B) -polymer block (A) in that good performance can be obtained as an elastomer material.
  • Those having a structure are preferred.
  • the polymer block (A) acts as a hard segment, and the polymer block (B) acts as a soft segment.
  • the present block copolymer exhibits excellent performance in mechanical properties such as elongation at break and strength at break.
  • the weight ratio of the polymer block (A) and the polymer block (B) in the present block copolymer is preferably 10:90 to 50:50, and may be 15:85 to 45:55. It may be 40:60.
  • the ratio of the polymer block (B) in the present block copolymer can be 50% by mass or more and 90% by mass or less, and may be 55% by mass or more and 85% by mass or less, or 60% by mass or more and 80% by mass. % Or less.
  • the SP value of the polymer block (A) and the SP value of the polymer block (B) preferably have a difference of 0.1 or more.
  • the difference in SP value may be 0.3 or more, 0.5 or more, 0.8 or more, or 1.0 or more. Further, from the viewpoint of manufacturing, etc., the difference in SP value is preferably 10 or less, and may be 5.0 or less.
  • the polymer block (A) and / or the block (B) in the block copolymer has a crosslinkable functional group
  • a material having excellent mechanical properties can be obtained by crosslinking using this. it can.
  • the cross-linking may be caused by a reaction between cross-linkable functional groups introduced into the polymer block (A)) and / or the block (B), or, as described later, a function capable of reacting with the cross-linkable functional group. You may carry out by adding the crosslinking agent which has group.
  • the number average molecular weight (hereinafter referred to as “Mn”) of the present block copolymer is preferably in the range of 5,000 to 400,000. If Mn is 5,000 or more, moderate strength can be exhibited. Moreover, if it is 400,000 or less, fluidity
  • Mn may be 10,000 or more, 20,000 or more, or 30,000 or more.
  • the upper limit of Mn may be 300,000 or less, 200,000 or less, or 100,000 or less.
  • the range of Mn may be, for example, 100,000 to 300,000, or 20,000 to 200,000.
  • the dispersity (hereinafter referred to as “Mw / Mn”) obtained by dividing the weight average molecular weight (hereinafter referred to as “Mw”) of the block copolymer by the value of Mn described above is the moldability. For example, it may be 3.0 or less.
  • the Mw / Mn may be 2.5 or less, 2.0 or less, 1.8 or less, or 1.5 or less.
  • the lower limit of Mw / Mn is 1.0, may be 1.05 or more, and may be 1.1.
  • the block copolymer of the present invention is not particularly limited as long as the block copolymer having the polymer block (A) and the polymer block (B) is obtained, and a known production method is adopted. be able to. Examples thereof include a method using various controlled polymerization methods such as living radical polymerization and living anion polymerization, a method of coupling polymers having functional groups, and the like. Among these, the living radical polymerization method is preferable because the operation is simple and the method can be applied to a wide range of monomers.
  • Living radical polymerization may employ any process such as a batch process, a semi-batch process, a dry continuous polymerization process, or a continuous stirred tank process.
  • the polymerization method can be applied to various modes such as bulk polymerization without using a solvent, solvent-based solution polymerization, aqueous emulsion polymerization, miniemulsion polymerization or suspension polymerization.
  • RAFT method reversible addition-cleavage chain transfer polymerization method
  • NMP method nitroxy radical method
  • Transfer radical polymerization method (hereinafter referred to as “ATRP method”), polymerization method using organic tellurium compound (hereinafter referred to as “TERP method”), polymerization method using organic antimony compound (hereinafter referred to as “SBRP method”).
  • Various polymerization methods such as a polymerization method using an organic bismuth compound (hereinafter referred to as “BIRP method”) and an iodine transfer polymerization method can be employed.
  • BIRP method organic bismuth compound
  • iodine transfer polymerization method a polymerization method using an organic bismuth compound
  • the ATRP method are preferable from the viewpoints of controllability of polymerization and ease of implementation.
  • RAFT agent a specific polymerization control agent
  • RAFT agent a specific polymerization control agent
  • RAFT agent various known RAFT agents such as a dithioester compound, a xanthate compound, a trithiocarbonate compound, and a dithiocarbamate compound can be used.
  • RAFT agent a monofunctional agent having only one active site may be used, or a bifunctional or more functional agent may be used.
  • a bifunctional RAFT agent is preferably used from the viewpoint of efficiently obtaining the block copolymer having the A- (BA) n type structure.
  • the usage-amount of a RAFT agent is suitably adjusted with the monomer to be used, the kind of RAFT agent, etc.
  • radical polymerization initiators such as azo compounds, organic peroxides and persulfates can be used.
  • An azo compound is preferred because side reactions are unlikely to occur.
  • Specific examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1- Carbonitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), and the like.
  • the radical polymerization initiator may be used alone or in combination of two or more.
  • the use ratio of the radical polymerization initiator is not particularly limited, but from the viewpoint of obtaining a polymer having a smaller Mw / Mn, the use amount of the radical polymerization initiator with respect to 1 mol of the RAFT agent is preferably 0.5 mol or less, More preferably, it is 0.2 mol or less. From the viewpoint of stably performing the polymerization reaction, the lower limit of the amount of the radical polymerization initiator used relative to 1 mol of the RAFT agent is 0.01 mol. Therefore, the amount of the radical polymerization initiator used relative to 1 mol of the RAFT agent is preferably in the range of 0.01 to 0.5 mol, and more preferably in the range of 0.05 to 0.2 mol.
  • the reaction temperature during the polymerization reaction by the RAFT method is preferably 40 to 100 ° C., more preferably 45 to 90 ° C., and further preferably 50 to 80 ° C. If reaction temperature is 40 degreeC or more, a polymerization reaction can be advanced smoothly. On the other hand, if reaction temperature is 100 degrees C or less, while being able to suppress a side reaction, the restrictions regarding the initiator and solvent which can be used are eased.
  • a specific alkoxyamine compound having nitroxide or the like is used as a living radical polymerization initiator, and polymerization proceeds via a nitroxide radical derived therefrom.
  • the type of nitroxide radical to be used is not particularly limited, but from the viewpoint of polymerization controllability when polymerizing an acrylate-containing monomer, a compound represented by the general formula (2) is used as the nitroxide compound. Is preferred.
  • R 1 is an alkyl group having 1 to 2 carbon atoms or a hydrogen atom
  • R 2 is an alkyl group having 1 to 2 carbon atoms or a nitrile group
  • R 3 is — (CH 2 ) m—, m Is 0 to 2
  • R 4 and R 5 are alkyl groups having 1 to 4 carbon atoms ⁇
  • the nitroxide compound represented by the general formula (2) is primarily dissociated by heating at about 70 to 80 ° C., and causes an addition reaction with the vinyl monomer.
  • a polyfunctional polymerization precursor by adding a nitroxide compound to a vinyl monomer having two or more vinyl groups.
  • the vinyl monomer can be living polymerized by secondary dissociation of the polymerization precursor under heating.
  • the polymerization precursor since the polymerization precursor has two or more active sites in the molecule, a polymer having a narrower Mw / Mn can be obtained.
  • a bifunctional polymerization precursor having two active sites in the molecule it is preferable to use a bifunctional polymerization precursor having two active sites in the molecule.
  • the usage-amount of a nitroxide compound is suitably adjusted with the kind etc. of the monomer to be used and a nitroxide compound.
  • the nitroxide radical represented by the general formula (3) is in the range of 0.001 to 0.2 mol with respect to 1 mol of the nitroxide compound represented by the general formula (2).
  • the polymerization may be carried out by adding in the above. ⁇ Wherein R 4 and R 5 are each an alkyl group having 1 to 4 carbon atoms. ⁇
  • Addition of 0.001 mol or more of the nitroxide radical represented by the general formula (3) shortens the time for the concentration of the nitroxide radical to reach a steady state. As a result, the polymerization can be controlled to a higher degree, and a polymer having a narrower Mw / Mn can be obtained. On the other hand, if the amount of the nitroxide radical added is too large, the polymerization may not proceed.
  • a more preferable addition amount of the nitroxide radical to 1 mol of the nitroxide compound is in the range of 0.01 to 0.5 mol, and a more preferable addition amount is in the range of 0.05 to 0.2 mol.
  • the reaction temperature in the NMP method is preferably 50 to 140 ° C., more preferably 60 to 130 ° C., still more preferably 70 to 120 ° C., and particularly preferably 80 to 120 ° C. If reaction temperature is 50 degreeC or more, a polymerization reaction can be advanced smoothly. On the other hand, if the reaction temperature is 140 ° C. or lower, side reactions such as radical chain transfer tend to be suppressed.
  • a polymerization reaction is generally performed using an organic halide as an initiator and a transition metal complex as a catalyst.
  • an organic halide as an initiator, a monofunctional one or a bifunctional or higher one may be used.
  • a bifunctional compound is preferably used from the viewpoint of efficiently obtaining the block copolymer having the A- (BA) n type structure.
  • bromide and chloride are preferable as the kind of halogen.
  • the reaction temperature in the ATRP method is preferably 20 to 200 ° C., more preferably 50 to 150 ° C. If reaction temperature is 20 degreeC or more, a polymerization reaction can be advanced smoothly.
  • A- (BA) n type structure such as an ABA triblock copolymer comprising a polymer block (A) -polymer block (B) -polymer block (A) by a living radical polymerization method
  • the target block copolymer may be obtained by sequentially polymerizing each block, but the target product can be obtained more efficiently when it is produced by a method including the following two-stage polymerization process. preferable.
  • polymer block (B) As a first polymerization step, after polymerizing a (meth) acrylic acid ester compound to obtain a polymer block (B), as a second polymerization step, an amide group-containing vinyl compound, a maleimide compound and an aromatic monomer Polymer block (A) is obtained by polymerizing at least one radically polymerizable monomer selected from the group consisting of isomers.
  • an ABA triblock copolymer comprising a polymer block (A) -acrylic polymer block (B) -polymer block (A) can be obtained. According to this method, a process can be simplified compared with the case where each block is polymerized in sequence.
  • higher order block copolymers such as a tetrablock copolymer
  • a tetrablock copolymer can be obtained by repeating said 1st polymerization process and 2nd polymerization process.
  • the block copolymer may be polymerized in the presence of a chain transfer agent, if necessary, regardless of the polymerization method.
  • a chain transfer agent known ones can be used. Specifically, ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 2-butanethiol, 1-hexanethiol, 2-hexane Thiol, 2-methylheptane-2-thiol, 2-butylbutane-1-thiol, 1,1-dimethyl-1-pentanethiol, 1-octanethiol, 2-octanethiol, 1-decanethiol, 3-decanethiol, 1-undecanethiol, 1-dodecanethiol, 2-dodecanethiol, 1-tridecanethiol, 1-tetradecanethiol, 3-methyl-3-undecanethiol, 5-ethyl-5-
  • a known polymerization solvent can be used in living radical polymerization.
  • aromatic compounds such as benzene, toluene, xylene and anisole
  • ester compounds such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate
  • ketone compounds such as acetone and methyl ethyl ketone
  • dimethylformamide, acetonitrile, dimethyl sulfoxide Examples include alcohol and water.
  • this block copolymer can be applied alone or as a molding resin material, it may be in the form of a composition containing known additives or the like, if necessary.
  • the block copolymer contains a crosslinkable functional group in at least one of the polymer block (A) and the polymer block (B), a crosslinking agent and a crosslinking accelerator capable of reacting with the functional group are blended. And it is preferable at the point which can obtain the molded article excellent in mechanical strength by performing heat processing etc. as needed.
  • this block copolymer contains the structural unit derived from the crosslinkable monomer which has a carboxyl group, as a crosslinking agent, a polyvalent amine, polyfunctional isocyanate, etc. are used preferably.
  • a polyvalent amine include aliphatic diamine compounds such as hexamethylene diamine, hexamethylene diamine carbamate and N, N′-dicinnamylidene-1,6-hexane diamine; 4,4′-methylenebiscyclohexylamine carbamate, etc.
  • Cycloaliphatic diamine compounds 4,4'-methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4 '-(m-phenylenediisopropylidene) dianiline, 4,4'-(p -Phenylenediisopropylidene) dianiline, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzanilide, m-xylylenediamine, p-xylylenediamine, 1, 3,5-benzenetriamine and 1,3,5-benzenetriamino Aromatic diamine compounds such as chill, and the like.
  • examples of the polyfunctional isocyanate include hexamethylene diisocyanate, dimethyldiphenylene diisocyanate, and isophorone diisocyanate.
  • guanidine compounds such as 1,3-di-o-tolylguanidine and 1,3-diphenylguanidine; imidazole compounds such as 2-methylimidazole and 2-phenylimidazole; phosphoric acid, carbonic acid, bicarbonate Salts of weak acids, such as alkali metal salts of acids such as stearic acid and lauric acid (Li, Na, K); thirds such as triethylenediamine and 1,8-diazabicyclo- [5.4.0] undecene-7 Tertiary amines; Tertiary phosphine compounds such as triphenylphosphine and tri (methyl) phenylphosphine; Cross-linking aids such as quaternary onium salts such as tetrabutylammonium bromide, tetrabutylammonium chloride and octadecyltri-n-butylammonium bromide It is preferable to
  • the block copolymer includes a structural unit derived from a crosslinkable monomer having an epoxy group
  • examples of the crosslinking agent include organic carboxylic acid ammonium salt, dithiocarbamate, polyvalent carboxylic acid or anhydride, A combination with a quaternary ammonium salt or a phosphonium salt is preferably used.
  • organic carboxylic acid ammonium salt include ammonium benzoate.
  • dithiocarbamate include zinc salts such as dimethyldithiocarbamic acid, diethyldithiocarbamic acid and dibenzyldithiocarbamic acid, iron salts and tellurium salts.
  • polyvalent carboxylic acid examples include malonic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, citric acid, tartaric acid and phthalic acid.
  • quaternary ammonium salt examples include tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, n-dodecyltrimethylammonium bromide and octadecyltrimethylammonium bromide.
  • Examples of the phosphonium salt include triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, triphenylbenzylphosphonium iodide, triethylbenzylphosphonium chloride, and tetrabutylphosphonium bromide.
  • this block copolymer contains the structural unit derived from the crosslinkable monomer which has a hydroxyl group, as a crosslinking agent, polyfunctional isocyanate etc. are used preferably.
  • polyfunctional isocyanate etc. are used as the block copolymer of the present invention.
  • the block copolymer of the present invention contains a structural unit derived from a crosslinkable monomer having a primary or secondary amino group, a polyfunctional isocyanate, a polyfunctional glycidyl compound, or the like is preferably used as the crosslinking agent.
  • this block copolymer contains a polymerizable unsaturated group
  • a dithiol compound such as 1,2-ethanedithiol, 1,4-butanethiol, 1,10-decanethiol, 1,4-benzenethiol, or ethane
  • An ene-thiol reaction with polyvalent thiols such as trithiol compounds such as -1,1,1-trithiol and 1,3,5-benzenetrithiol can be used.
  • the crosslinkable group of the present block copolymer is a reactive silicon group, a crosslinking reaction is caused by moisture, so there is no need to add a crosslinking agent or the like.
  • additives include tackifiers, plasticizers, oils, anti-aging agents, inorganic fillers, pigments, antioxidants, and ultraviolet absorbers.
  • the amount of the additive is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and further preferably 0 to 2% by mass with respect to the present block copolymer.
  • thermoplastic resins may be added for the purpose of adjusting the performance or processability of the molding resin composition containing the block copolymer of the present invention.
  • thermoactive resin include polyolefin resins such as polyethylene and polypropylene, polystyrene styrene resins, vinyl resins such as polyvinyl chloride, polyester resins, and polyamide resins.
  • the molding resin composition containing the block copolymer of the present invention exhibits good fluidity when heated to about 150 to 300 ° C. For this reason, it can be applied to molding processing by various methods of melt extrusion molding, melt injection molding, and melt casting. By cooling the obtained molded product to near room temperature, the molded product exhibits excellent mechanical performance. Moreover, the molded article obtained from the molding resin composition of the present invention can be excellent in heat resistance and oil resistance.
  • composition ratio of polymer> The composition ratio of the obtained polymer was identified and calculated from 1 H-NMR measurement.
  • Tg of the obtained polymer was determined from the intersection of the base line of the heat flux curve obtained using a differential scanning calorimeter and the tangent at the inflection point.
  • the heat flux curve shows that about 10 mg of a sample was cooled to ⁇ 50 ° C. and held for 5 minutes, then heated to 300 ° C. at 10 ° C./min, subsequently cooled to ⁇ 50 ° C. and held for 5 minutes, then 10 ° C. / It was obtained under conditions where the temperature was raised to 350 ° C. in min.
  • the polymer obtained in each of the production examples was used as a sample for the Tg of the polymer block (B).
  • Tg of a polymer block (A) is obtained (with Tg of an acrylic polymer block (B)) by using the block copolymer obtained in the Example and the comparative example as a sample.
  • ⁇ Initial tensile properties 100 parts of a block copolymer and 0.3 parts of Irganox 1010 (manufactured by BASF) as an antioxidant were dissolved in tetrahydrofuran (THF) to prepare a solution having a polymer concentration of 10%. This was poured into a mold, and THF was dried and distilled off to produce a film having a thickness of about 1 mm. Using the film obtained above as a sample, the tensile strength at break and elongation at break (25 ° C.) were measured according to JIS K 6251.
  • Formability A molded body of 125 mm ⁇ 125 mm ⁇ thickness 2 mm was injection molded under the following conditions, and the moldability under heating was evaluated. The result was determined based on the following criteria. Injection molding machine: 100MSIII-10E manufactured by Mitsubishi Heavy Industries, Ltd. Injection molding temperature: 240 ° C Injection pressure: 30% Injection time: 3 sec Mold temperature: 40 °C ⁇ Criteria >> A: The surface state of the molded body was good, and a molded body having a uniform size was obtained. O: A slightly uneven flow was observed on the surface, but a molded body having a uniform size was obtained.
  • Production Examples 2-6 (Production of polymers B, C, D, E, F) Polymers B to F were obtained in the same manner as in Production Example 1 except that the amount of DLBTTC was as shown in Table 1 and that the reaction time was appropriately adjusted. The molecular weight of each polymer was measured and shown in Table 1.
  • the block copolymer 1 is a triblock copolymer having a structure of polymer block (A) -polymer block (B) -polymer block (A).
  • the physical property values of the block copolymer 1 are shown in Table 3.
  • Synthesis example 7 (Production of block copolymer 7) A 1 L flask equipped with a stirrer and a thermometer was charged with the polymer G (100.0 g), N-phenylmaleimide (25.0 g), styrene (15.0 g) and anisole (100 g) obtained in Production Example 7, The mixture was sufficiently deaerated by nitrogen bubbling, and polymerization was started in a thermostatic bath at 110 ° C. After 5 hours, the reaction was stopped by cooling to room temperature. The polymerization solution was purified by reprecipitation from methanol and vacuum dried to obtain block copolymer 7.
  • the molecular weight of the obtained block copolymer 7 was Mn 29,400, Mw 43,800, and Mw / Mn was 1.49 from GPC measurement.
  • the block copolymer 7 is a triblock copolymer having a structure of polymer block (A) -polymer block (B) -polymer block (A).
  • the physical property values of the block copolymer 7 are shown in Table 3.
  • PA-1437B Melt viscosity 4.2 Pa ⁇ s (220 ° C), softening point 192 ° C
  • Polyolefin resin PO-1 (PPET-6427 manufactured by Toagosei Co., Ltd.) Melt viscosity 45Pas (220 ° C), softening point 165 ° C
  • Polyester resin PES-1 (PES-M180 manufactured by Toagosei Co., Ltd.) Melt viscosity 30Pa ⁇ s (210 °C), softening point 200 °C
  • Examples 1 to 11 correspond to molding compositions containing the present block copolymer, all having excellent moldability and good values for heat resistance and oil resistance.
  • Comparative Examples 1 to 3 using hot melt type polyamide resin, polyolefin resin and polyester resin were inferior in heat resistance and oil resistance, and moldability was not sufficient.
  • Comparative Example 4 does not include a structural unit derived from an amide group-containing vinyl compound, a maleimide compound, and an aromatic monomer in the polymer block (A), which is a hard segment, in terms of heat resistance and oil resistance. Insufficient results were obtained.
  • the molding resin composition containing the present block copolymer is excellent in heat resistance and oil resistance and exhibits good melt moldability. For this reason, it is useful as a hot melt type molding agent.
  • the molding resin composition of the present invention can provide a material that sufficiently satisfies various performances (heat resistance, oil resistance, moisture resistance, adhesiveness, moldability) for molding an electronic component having a complicated shape. For example, it is useful for molding of connectors, harnesses or electronic components used in automobiles, communications, computers, various household appliances, switches having printed circuit boards, sensors, and the like.

Abstract

L'invention fournit une composition pour moulage qui consiste en une composition de résine thermoplastique d'une excellente aptitude au moulage et permettant une mise en œuvre en tant qu'adhésif thermofusible, et qui se révèle excellente en termes de résistance à la chaleur et de résistance à l'huile. Plus précisément, l'invention concerne une composition de résine pour moulage qui comprend un copolymère séquencé possédant une séquence polymère (A) et une séquence polymère (B). Ladite séquence polymère (A) présente une température de transition vitreuse (Tg) supérieure ou égale à 50°C, et possède une unité structurale dérivée d'au moins une sorte de monomère polymérisable par voie radicalaire choisie dans un groupe constitué d'un composé vinyle comprenant un groupe amide, d'un composé maléimide et d'un monomère aromatique. Ladite séquence polymère (B) présente une Tg inférieure ou égale à -10°C, et contient une unité structurale dérivée d'un composé ester (méth)acrylique.
PCT/JP2017/021640 2016-06-13 2017-06-12 Composition de résine pour moulage, et article moulé WO2017217363A1 (fr)

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JP2018053044A (ja) * 2016-09-27 2018-04-05 株式会社日本触媒 ブロック共重合体
JP2019112590A (ja) * 2017-12-26 2019-07-11 東亞合成株式会社 重合体の製造方法
WO2020149388A1 (fr) * 2019-01-16 2020-07-23 積水フーラー株式会社 Copolymere sequence reticulable et adhesif thermofusible
WO2020149385A1 (fr) * 2019-01-16 2020-07-23 積水フーラー株式会社 Copolymère séquencé réticulable et agent de revêtement
JPWO2020149387A1 (ja) * 2019-01-16 2021-02-18 積水フーラー株式会社 架橋性ブロック共重合体及びその製造方法並びに伸縮性部材

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JP2018053044A (ja) * 2016-09-27 2018-04-05 株式会社日本触媒 ブロック共重合体
JP2019112590A (ja) * 2017-12-26 2019-07-11 東亞合成株式会社 重合体の製造方法
JP7024395B2 (ja) 2017-12-26 2022-02-24 東亞合成株式会社 重合体の製造方法
WO2020149388A1 (fr) * 2019-01-16 2020-07-23 積水フーラー株式会社 Copolymere sequence reticulable et adhesif thermofusible
WO2020149385A1 (fr) * 2019-01-16 2020-07-23 積水フーラー株式会社 Copolymère séquencé réticulable et agent de revêtement
JPWO2020149385A1 (ja) * 2019-01-16 2021-02-18 積水フーラー株式会社 架橋性ブロック共重合体及びコーティング剤
JPWO2020149388A1 (ja) * 2019-01-16 2021-02-18 積水フーラー株式会社 架橋性ブロック共重合体及びホットメルト粘着剤
JPWO2020149387A1 (ja) * 2019-01-16 2021-02-18 積水フーラー株式会社 架橋性ブロック共重合体及びその製造方法並びに伸縮性部材
JP7289148B2 (ja) 2019-01-16 2023-06-09 積水フーラー株式会社 架橋性ブロック共重合体及びホットメルト粘着剤

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