WO2023090308A1 - 樹脂組成物およびその用途 - Google Patents

樹脂組成物およびその用途 Download PDF

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Publication number
WO2023090308A1
WO2023090308A1 PCT/JP2022/042338 JP2022042338W WO2023090308A1 WO 2023090308 A1 WO2023090308 A1 WO 2023090308A1 JP 2022042338 W JP2022042338 W JP 2022042338W WO 2023090308 A1 WO2023090308 A1 WO 2023090308A1
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Prior art keywords
group
ethylene
resin composition
resin
zirconium dichloride
Prior art date
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Ceased
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PCT/JP2022/042338
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English (en)
French (fr)
Japanese (ja)
Inventor
涼 立松
昌太 阿部
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Priority to KR1020247005044A priority Critical patent/KR20240035555A/ko
Priority to US18/686,585 priority patent/US20240352253A1/en
Priority to EP22895589.4A priority patent/EP4435047A1/en
Priority to JP2023561593A priority patent/JPWO2023090308A1/ja
Priority to CN202280076106.2A priority patent/CN118251454A/zh
Publication of WO2023090308A1 publication Critical patent/WO2023090308A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F210/06—Propene
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/10—Homopolymers or copolymers of propene
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D175/08—Polyurethanes from polyethers
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    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L2314/00—Polymer mixtures characterised by way of preparation
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Definitions

  • the present invention relates to resin compositions and uses thereof.
  • Curable urethane resins are widely used in thermosetting moldings, paints, room temperature curing moldings, injections, paints and coating materials. Cured products obtained by curing epoxy resins are widely used as electrical and electronic insulating materials, paints, adhesives, casting materials, etc., due to their excellent heat resistance, electrical properties, and mechanical properties. ing. In these applications, various defects such as bubbles, cissing, and craters may occur on the cured surface during molding or coating, which may impair the finish of the cured surface. Defoamers are used as a countermeasure. There are many things. These antifoaming agents have the characteristics of either improving the surface activity or deteriorating the compatibility, that is, the effect of incompatibility.
  • Patent Document 1 discloses an antifoaming agent composed of an acrylic/vinyl ether copolymer
  • Patent Document 2 discloses an antifoaming agent composed of a vinyl ether polymer.
  • silicone-based antifoaming agents with high surfactant effects exhibit good antifoaming effects even when added in small amounts, they are the main cause of the cissing and cratering phenomena referred to in the paint industry, and greatly impair the appearance of the cured surface.
  • Acrylic/vinyl ether copolymer antifoaming agents, modified butadiene polymer antifoaming agents, and vinyl ether polymer antifoaming agents may not provide sufficient antifoaming effects depending on the viscosity of the system and the presence or absence of a solvent. rice field.
  • Patent Documents 3 to 6 disclose resins that can form cured products with excellent surface appearance without foaming of molded products or coating films during curing by using ethylene/ ⁇ -olefin copolymers as antifoaming agents. Compositions can be provided.
  • the performance of antifoaming agents mixed in resins is generally classified into antifoaming properties to suppress foaming and foam breaking properties to eliminate generated bubbles. If the foam suppressing property is insufficient, the appearance of the surface of the resin molding may be impaired due to the traces of bubbles that have disappeared. may be
  • an object of the present invention is to provide a resin composition containing an ethylene/ ⁇ -olefin copolymer as an antifoaming agent and having excellent foam breaking properties as well as foam suppressing properties.
  • the present invention relates to, for example, the following [1] to [18].
  • [1] Contains resin (X) (excluding copolymer (Y) described later) and ethylene/ ⁇ -olefin copolymer (Y) satisfying the following requirements (y-1) and (y-2) resin composition.
  • (y ⁇ 1) The solubility parameter calculated based on DW Van Krevelen's estimation method is 15.5 to 16.3 (MPa) 1/2 .
  • (y-2) Weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 1,500 to 30,000.
  • (y-4) Ethylene content is 1 to 40 mol %.
  • [3] Contains resin (X) (excluding copolymer (Y) described later) and ethylene/ ⁇ -olefin copolymer (Y) satisfying the following requirements (y-2) and (y-4) resin composition.
  • (y-2) Weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 1,500 to 30,000.
  • (y-4) Ethylene content is 1 to 40 mol %.
  • curable resin (X1) is one or more resins selected from the group consisting of epoxy resins, urethane resins, unsaturated polyesters, phenol resins, melamine resins and silicone resins.
  • a paint comprising the resin composition according to any one of [1] to [10].
  • the resin (X) (excluding the copolymer (Y') described later) and the method ( ⁇ ) below, and the following requirements (y-1) and (y-2), or the following requirements (A method for producing a resin composition comprising the step of mixing an ethylene/ ⁇ -olefin copolymer (Y') that satisfies y-2) and (y-4).
  • y ⁇ 1 The solubility parameter calculated based on DW Van Krevelen's estimation method is 15.5 to 16.3 (MPa) 1/2 .
  • Weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 1,500 to 30,000.
  • Ethylene content is 1 to 40 mol %.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 are each independently a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group; , a plurality of adjacent groups may be linked to each other to form a ring structure, R 6 and R 11 are the same group and are a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, R 7 and R 10 are the same group and are a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, R 6 and R 7 may combine with a hydrocarbon having 2 to 3 carbon atoms to form a ring structure, R 10 and R 11 may combine with a hydrocarbon having 2 to 3 carbon atoms to form a ring structure, and R 6 , R 7 , R 10 and R 11 are not hydrogen atoms at the same time, Y is a carbon atom or a silicon atom, R 13 and R 14 are each independently a hydrogen atoms at the same time
  • Both the substituents R 13 and R 14 of the bridged metallocene compound (P) represented by the above (formula 1) are aryl groups, and one of the substituents R 2 and R 3 is a saturated carbon having 4 carbon atoms.
  • the resin composition of the present invention is excellent not only in its foam-breaking properties but also in its foam-suppressing properties. Therefore, the resin composition of the present invention can be preferably used for coating applications such as paints, elastic coating materials, and waterproof materials.
  • the resin composition according to the present invention contains a resin (X) and an ethylene/ ⁇ -olefin copolymer (Y).
  • Resin (X) is a resin other than copolymer (Y), which will be described later.
  • examples of the resin (X) include curable resin (X1) and thermoplastic resin (X2), and curable resin (X1) is preferred from the viewpoint of excellent heat resistance and water resistance.
  • Curable resin (X1) examples include one or more resins selected from the group consisting of epoxy resins, urethane resins, unsaturated polyesters, phenol resins, melamine resins and silicone resins. Among these, the curable resin (X1) is preferably one or more resins selected from the group consisting of urethane resins and epoxy resins from the viewpoint of excellent adhesion to other substances.
  • Urethane resin The urethane resin exemplified as the curable resin (X1) may be various curable urethane resins including conventionally known ones. Urethane resins are generally classified into a one-component curing type in which a compound containing an active hydrogen group and an excess of organic polyisocyanate react in the presence of moisture in the air to cure, and a component A containing an organic polyisocyanate and containing active hydrogen groups. It consists of a B liquid containing a compound, and is broadly classified into a two-component curing type in which the A liquid and the B liquid are weighed and mixed in a predetermined ratio just before use to cure.
  • the urethane resin may be of either a one-component curing type or a two-component curing type, and the two-component curing type is preferable from the viewpoint that the curing speed can be easily adjusted.
  • the organic polyisocyanate contained in the liquid A has an average of two or more isocyanate groups in one molecule.
  • organic polyisocyanates are not particularly limited, for example, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate aromatic diisocyanates such as isocyanates, 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; aromatic ring-containing aliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate; trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-prop
  • aromatic diisocyanates are preferred, and further 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate or mixtures thereof, 4,4′-diphenylmethane diisocyanate, carbodiimide-modified 4,4′-diphenylmethane Diisocyanates, polymethylene polyphenyl polyisocyanates are preferred.
  • the active hydrogen group-containing compound contained in the liquid B is not particularly limited, but examples thereof include polyamines and polyols.
  • polyamine is mainly used as an active hydrogen group-containing compound
  • urea is a curable resin in which an active hydrogen group-containing compound and an organic polyisocyanate are bonded mainly by urea bonds.
  • Polyol is mainly used as the resin and active hydrogen group-containing compound
  • a curable resin in which an active hydrogen group-containing compound and an organic polyisocyanate are combined mainly with urethane bonds is sometimes called urethane resin.
  • both are generically referred to as urethane resin without distinguishing between them.
  • polyamine examples include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, polyoxyalkylenepolyamines; Alicyclic polyamines such as isophoronediamine, norbornenediamine, hydrogenated xylylenediamine; aromatic ring-containing aliphatic polyamines such as xylylenediamine; 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 4,4′-diaminodiphenylmethane, 2,4-tolylenediamine, 2,6-tolylenediamine, 1,1'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 1,1',2,2'-tetrachloro-4,4'--
  • polyol examples include Ethylene glycol, propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, neopentyl glycol, alkanediol (carbon number: 7-22), diethylene glycol , triethylene glycol, dipropylene glycol, cyclohexanedimethanol, alkane-1,2-diol (carbon number: 17-20), hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl- low-molecular-weight diols such as 1-octene-3,8-diol, bishydroxyethoxybenzene, xylene glycol, bishydroxyethylene terephthalate, bisphenol A, bisphenol F; Glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-
  • polyols that can be the active hydrogen group-containing compound are obtained by an addition reaction of the above low-molecular-weight diols, low-molecular-weight triols, diamines or polyfunctional polyamines having three or more functional groups with alkylene oxides such as ethylene oxide and propylene oxide.
  • Polyester polyols obtained by ring-opening polymerization of lactones such as ⁇ -caprolactone and ⁇ -valerolactone using the low-molecular-weight diols and low-molecular-weight triols as starting materials;
  • a polycarbonate polyol obtained by ring-opening polymerization of ethylene carbonate using the low-molecular-weight diol or low-molecular-weight triol as a starting material; at least one polyol selected from the group consisting of the low-molecular-weight diols and low-molecular-weight triols, oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3- At least one selected from the group consisting of dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, sebacic acid, other alipha
  • carboxylic acid derivatives examples include acid anhydrides such as oxalic anhydride, succinic anhydride, 2-alkyl anhydride (carbon number: 12 to 18) succinic acid, oxalic acid dichloride, adipic acid chloride, and sebacic acid chloride. and acid halides such as
  • the active hydrogen group-containing compound may be used singly or in combination of two or more.
  • the active hydrogen group-containing compound preferably includes polyoxyethylene polyols, polyoxyethylene propylene polyols, polyoxypropylene polyols, bisphenol-based compounds having 2 to 4 active hydrogen groups in one molecule and an average molecular weight of 200 to 6000. Polyols, castor oil polyols.
  • polyols are preferable from the viewpoint of obtaining cured products with excellent flexibility.
  • a combination of two or more compounds selected from polyols having 2 to 4 active hydrogen groups per molecule is preferred.
  • polyamine is preferable from the viewpoint of excellent curing reaction speed, especially at low temperatures, and excellent chemical stability of the cured product.
  • preferred examples of polyamines include polyoxyalkylenediamines and polyoxyalkylenetriamines having one or more amino groups in one molecule and having an average molecular weight of 200 to 6000. More specifically, polyoxyalkylenetriamines having a polypropylene glycol chain A diamine having a structure in which the terminal hydroxyl group is substituted with an amino group, and a triamine having a structure in which the terminal hydroxyl group of a polyol is substituted with an amino group, which is obtained by dehydration condensation of polypropylene glycol with a trihydric alcohol such as glycerin. be done.
  • such polyoxyalkylenediamines and polyoxyalkylenetriamines can be used in combination with the aforementioned polyamines.
  • a two-component curable urethane resin can be preferably employed as the urethane resin as the curable resin (X1).
  • an excess of the organic polyisocyanate can be used without limitation, but a prepolymer having at least one free isocyanate group in one molecule obtained by reaction with the active hydrogen group-containing compound is used. is preferred.
  • an organic polyisocyanate and an active hydrogen group-containing compound are mixed under a nitrogen gas atmosphere so that the number of active hydrogen groups in the active hydrogen group-containing compound is 0.1 to 0.1 per isocyanate group of the organic polyisocyanate.
  • a ratio of 2.0 is prepared by reacting at a temperature of 40-120° C. for 4-8 hours under stirring.
  • the urethane prepolymer thus obtained preferably has an isocyanate group content of 1 to 20% by weight, preferably 2 to 10% by weight.
  • the active hydrogen group-containing compound used in the liquid B the active hydrogen group-containing compounds described above, such as polyamines and polyols, can be used without particular limitation. It is preferable to use a prepolymer having at least one active hydrogen group-containing compound per molecule obtained by reacting the organic polyisocyanate with an excess of the active hydrogen group-containing compound.
  • the A liquid and the B liquid preferably have 0.1 to 2 active hydrogen groups (hydroxyl groups and/or amino groups) in the active hydrogen group-containing compound per one isocyanate group in the organic polyisocyanate, More preferably 0.5 to 1.5 pieces, more preferably 0.8 to 1.2 pieces are mixed.
  • Epoxy resin As the epoxy resin exemplified as the curable resin (X1), known epoxy resins can be used without particular limitation as long as they are liquid at room temperature (for example, 25°C). Specifically, glycidyl ether type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, hydrogenated bisphenol A type liquid epoxy resin; glycidyl ester type epoxy resin such as hexahydro phthalic acid glycidyl ester, dimer acid glycidyl ester; glycidylamine-type epoxy resins, such as triglycidyl isocyanurate, tetraglycidyldiaminodiphenylmethane; linear aliphatic epoxides, such as epoxidized polybutadiene, epoxidized soybean oil; alicyclic epoxysides , for example, 3,4-epoxy-6-methylcyclohexylmethyl carboxy
  • the epoxy resin may be a mixture of liquid epoxy resin and various solid epoxy resins, which is heated and mixed to be liquefied, as long as the effects of the present invention are not impaired.
  • the epoxy resin may be adjusted to a desired viscosity by adding a low-viscosity aliphatic epoxy compound.
  • such a low-viscosity aliphatic epoxy compound is a glycidyl ether of a polyhydric alcohol or a glycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to a polyhydric alcohol, for example, Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and pentaerythritol poly glycidyl ethers of aliphatic polyhydric alcohols, such as glycidyl ethers, hydrogenated bisphenol A diglycidyl ether; Glycidyl ethers of aliphatic
  • the epoxy compound used for the purpose of reducing the viscosity of the epoxy resin in the present invention is not limited to the low-viscosity aliphatic epoxy compound.
  • Aromatic glycidylamines with relatively low viscosity such as those having relatively low viscosity, may also be used. These epoxy compounds may be used singly or in combination of two or more.
  • thermoplastic resin (X2) examples include Polyolefins such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polybutene, cyclic olefin polymer, ethylene-propylene copolymer, cyclic olefin copolymer; Styrenic polymers such as polystyrene, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, and hydrogenated products thereof; polyvinyl chloride, polyvinylidene chloride; Vinyl carboxylic acid polymers and vinyl carboxylic acid ester polymers such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate, and polyethyl methacrylate
  • the ethylene/ ⁇ -olefin copolymer (Y) is an ethylene/ ⁇ -olefin copolymer that satisfies requirements (y-1) and (y-2) described later.
  • the ethylene/ ⁇ -olefin copolymer (Y) preferably satisfies requirement (y-4) described later, and preferably satisfies requirements (y-3) and (y-5) described later.
  • the ethylene/ ⁇ -olefin copolymer (Y) is an ethylene/ ⁇ -olefin copolymer that satisfies requirements (y-2) and (y-4) described later. be.
  • the ethylene/ ⁇ -olefin copolymer (Y) can satisfy the following requirements (y-1) to (y-5).
  • the solubility parameter calculated based on DW Van Krevelen's estimation method is 15.5-16.3 (MPa) 1/2 .
  • the estimation method is based on cohesive energies and molar molecular volumes (DW Van Krevelen, Klaast te Nijenhuis, "Properties of Polymers, Fourth Edition” Elsevier Science, 2009).
  • Said solubility parameter is preferably in the range of 15.8-16.3 (MPa) 1/2 , more preferably in the range of 16.0-16.3 (MPa) 1/2 .
  • the solubility parameter is smaller than the above lower limit, especially 15.5 (MPa) 1/2 , the ethylene/ ⁇ -olefin copolymer has low interfacial tension and low compatibility, resulting in poor foam breakability.
  • the composition containing the resin (X) and the ethylene/ ⁇ -olefin copolymer and the cured product thereof tend to bleed out.
  • the solubility parameter is greater than the above upper limit, especially 16.3 (MPa) 1/2 , the ethylene/ ⁇ -olefin copolymer has high interfacial tension and high compatibility, and therefore has antifoaming properties.
  • the compatibility with the curable resin (X1) may be reduced, and may cause bleeding out, and the composition containing the resin (X) and an ethylene / ⁇ -olefin copolymer In addition, it may bleed out on the surface of the cured product and impair the appearance.
  • the value of the solubility parameter can be adjusted, for example, by changing the amount of ethylene supplied, the amount of hydrogen supplied, the amount of catalyst supplied, etc. during production.
  • Requirement (y-2) It has a weight average molecular weight (Mw) of 1,500 to 30,000 as determined by gel permeation chromatography (GPC) measured under the conditions employed in Examples described later.
  • the weight average molecular weight (Mw) is preferably in the range of 1,500 to 13,500, more preferably 1,500 to 11,000, even more preferably 1,500 to 8,500.
  • the weight-average molecular weight (Mw) is less than the above lower limit, particularly 1,500, the ethylene/ ⁇ -olefin copolymer may have too high compatibility and may not develop antifoaming properties. Since it contains a molecular weight component, it tends to bleed out to the surface of the composition containing the resin (X) and the ethylene/ ⁇ -olefin copolymer and the cured product thereof.
  • the weight average molecular weight exceeds the above upper limit, especially 30,000, the compatibility of the ethylene/ ⁇ -olefin copolymer with the resin (X) decreases, and the resin (X) and ethylene ⁇ Bleeding out may occur in compositions containing ⁇ -olefin copolymers and cured products thereof.
  • the kinematic viscosity at 100° C. measured according to ASTM D445 is 10 to 5,000 mm 2 /s.
  • the kinematic viscosity is preferably 15 to 3,500 mm 2 /s, more preferably 20 to 2,500 mm 2 /s, even more preferably 20 to 1,000 mm 2 /s, still more preferably 20 to 650 mm 2 /s. is.
  • the kinematic viscosity is at least the above lower limit, bleeding out of the ethylene/ ⁇ -olefin copolymer (Y) onto the surface of the composition of the present invention and its cured product is suppressed.
  • the kinematic viscosity is equal to or less than the upper limit, the ethylene/ ⁇ -olefin copolymer (Y) has good dispersibility in the resin (X) and is easily incorporated into the foam film. Exhibits good defoaming properties.
  • ethylene content The ratio of structural units derived from ethylene (hereinafter also referred to as "ethylene content”) is 1 to 40 mol% (provided that the total amount of structural units in the ethylene/ ⁇ -olefin copolymer (Y) is 100 mol %). Said ethylene content preferably ranges from 2 to 39 mol %, more preferably from 3 to 38 mol %, even more preferably from 4 to 37 mol %.
  • the crystalline component of the ethylene/ ⁇ -olefin copolymer (Y) does not impair the appearance of the surface of the molded article formed from the composition of the present invention, and the composition of the present invention does not deteriorate.
  • the coating film formed from the material has good mechanical properties.
  • the said ethylene content is below the said upper limit, it is excellent in antifoaming property.
  • the ethylene content is preferably in the range of 5 to 29 mol%, more preferably 6 to 28 mol%, still more preferably 10 to 27 mol%, from the viewpoint of the balance between foam breaking property and foam suppressing property.
  • Tm melting point
  • ⁇ H heat of fusion
  • DSC differential scanning calorimetry
  • the melting point (Tm) and heat of fusion ( ⁇ H) of the ethylene/ ⁇ -olefin copolymer (Y) were measured by a differential scanning calorimeter (DSC) under the conditions employed in the examples described later. It is obtained by analyzing with reference to JIS K7121 from the DSC curve when the temperature is increased from -100°C to 150°C at a heating rate of 10°C/min.
  • the ethylene/ ⁇ -olefin copolymer (Y) satisfying the requirement (y-5) can be produced, for example, by adjusting the amount of ethylene supplied, the amount of hydrogen supplied, the amount of catalyst supplied, and the like. If the melting point of the ethylene/ ⁇ -olefin copolymer (Y) is not observed, then the ethylene/ ⁇ -olefin copolymer (Y) has good dispersibility in the resin (X) and does not enter the foam film. Since it is easily incorporated, it exhibits good defoaming properties.
  • the ethylene/ ⁇ -olefin copolymer (Y) satisfying the requirements (y-1) and (y-2) is preferably the requirement (y-3), the requirement (y-4), the requirement (y-5), Said requirement (y-3) and said requirement (y-4), Said requirement (y-3) and said requirement (y-5), Said requirement (y-4) and said requirement (y-5), or said requirement (y-3), said requirement (y-4) and said requirement (y-5) satisfy either
  • the ethylene/ ⁇ -olefin copolymer (Y) satisfying the requirements (y-2) and (y-4) is preferably the requirement (y-1), the requirement (y-3), Said requirement (y-5), or said requirement (y-1) and said requirement (y-3) Said requirement (y-1) and said requirement (y-5) Said requirement (y-3) and said requirement (y-5) satisfy either
  • Examples of the ⁇ -olefins constituting the ethylene/ ⁇ -olefin copolymer (Y) include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tricene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1- ⁇ -olefins having 3 to 20 carbon atoms such as octadecene, 1-nonadecene, and 1-eicosene. These ⁇ -olefins can be used singly or in combination of two or more.
  • the ⁇ -olefin preferably has 3 to 10 carbon atoms from the viewpoint of effectively reducing the crystallinity of the ethylene/ ⁇ -olefin copolymer (Y) and improving the dispersibility in the resin (X). It is an ⁇ -olefin, more preferably propylene, 1-butene or 1-pentene, and still more preferably propylene.
  • the ethylene/ ⁇ -olefin copolymer (Y) can be produced using known methods without limitation.
  • ethylene and ⁇ -olefin are copolymerized in the presence of a catalyst comprising a transition metal compound such as vanadium, zirconium, titanium, hafnium, an organoaluminum compound (organoaluminumoxy compound) and/or an ionized ionic compound. method.
  • Metallocene catalysts using transition metal compounds such as zirconium, titanium, and hafnium reduce the amount of 2,1-bonds (inversion) of two or more consecutive propylene monomers, improving the low-temperature properties of the curable resin composition.
  • Such methods are described in, for example, WO 2000/34420, JP-A-62-121710, WO-2004/29062, JP-A-2004-175707, WO-2001/27124, etc. .
  • the ethylene and ⁇ -olefin which are the monomers constituting the ethylene/ ⁇ -olefin copolymer (Y), may be, for example, fossil fuel-derived monomers or biomass-derived monomers, and these monomers may be used alone. or two or more of them may be used in combination.
  • the ethylene/ ⁇ -olefin copolymer (Y) may be composed only of a fossil fuel-derived monomer, may be composed only of a biomass-derived monomer, or may be composed of a fossil fuel-derived monomer and a biomass-derived monomer. may be used together.
  • Fossil fuels are oil, coal, natural gas, shale gas, or combinations thereof.
  • Biomass is any renewable natural raw material and its residues, such as of plant or animal origin, including fungi, yeasts, algae and bacteria.
  • the ethylene/ ⁇ -olefin copolymer (Y) includes a bridged metallocene compound (P) represented by the following general formula [I], an organometallic compound (Q-1), an organoaluminum oxy compound (Q-2 ) and a compound (Q-3) that forms an ion pair by reacting with the bridged metallocene compound (P) in the presence of an olefin polymerization catalyst containing ethylene and It can be produced by copolymerizing an ⁇ -olefin having 3 to 20 carbon atoms.
  • P bridged metallocene compound represented by the following general formula [I]
  • Q-1 organometallic compound
  • Q-2 organoaluminum oxy compound
  • Q-3 a compound that forms an ion pair by reacting with the bridged metallocene compound (P) in the presence of an olefin polymerization catalyst containing ethylene and It can be produced by copolymerizing an ⁇ -olefin having 3 to 20 carbon atom
  • ⁇ Y ⁇ Y is a carbon atom or a silicon atom, preferably a carbon atom.
  • ⁇ M ⁇ M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.
  • R1 ⁇ R14 ⁇ R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 are each independently an atom or substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group and a plurality of adjacent groups may be linked to each other to form a ring structure.
  • hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms, saturated cyclic hydrocarbon groups having 3 to 20 carbon atoms, chain unsaturated hydrocarbon groups having 2 to 20 carbon atoms, and cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms.
  • hydrocarbon groups include hydrocarbon groups, alkylene groups having 1 to 20 carbon atoms, arylene groups having 6 to 20 carbon atoms, and the like.
  • alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group and n-hexyl.
  • the number of carbon atoms in the alkyl group is preferably 1-6.
  • saturated cyclic hydrocarbon group having 3 to 20 carbon atoms examples include a saturated cyclic hydrocarbon group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4, which are groups in which the hydrogen atoms of a cyclic saturated hydrocarbon group are replaced with hydrocarbon groups having 1 to 17 carbon atoms, such as 2-adamantyl group -cyclohexylcyclohexyl group, 4-phenylcyclohexyl group and the like.
  • the cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.
  • chain unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group). and the like, which are alkynyl groups such as ethynyl group, 1-propynyl group and 2-propynyl group (propargyl group).
  • the chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.
  • cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclic unsaturated hydrocarbon groups such as cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group and anthracenyl group.
  • alkylene group having 1 to 20 carbon atoms examples include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, methylethylene group, n-propylene group and the like.
  • the alkylene group preferably has 1 to 6 carbon atoms.
  • arylene groups having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group and 4,4'-biphenylylene group.
  • the arylene group preferably has 6 to 12 carbon atoms.
  • silicon-containing hydrocarbon groups examples include alkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a triisopropylsilyl group, which are groups in which the carbon atoms in the above hydrocarbon groups are replaced with silicon atoms. , a dimethylphenylsilyl group, a methyldiphenylsilyl group, a t-butyldiphenylsilyl group and other arylsilyl groups, a pentamethyldisilanyl group, a trimethylsilylmethyl group, and the like.
  • the alkylsilyl group preferably has 1 to 10 carbon atoms
  • the arylsilyl group preferably has 6 to 18 carbon atoms.
  • R 6 and R 11 are the same group and are a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and the details of the hydrocarbon group and the silicon-containing hydrocarbon group are as described above.
  • R 7 and R 10 are the same group and are a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and the details of the hydrocarbon group and the silicon-containing hydrocarbon group are as described above.
  • R 6 and R 7 may combine with a hydrocarbon having 2 to 3 carbon atoms to form a ring structure
  • R 10 and R 11 may combine with a hydrocarbon having 2 to 3 carbon atoms to form a ring structure. may form R 6 , R 7 , R 10 and R 11 are not hydrogen atoms at the same time.
  • R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and may be linked together to form a ring structure.
  • the details of the hydrocarbon groups and silicon-containing hydrocarbon groups are as described above, and the hydrocarbon groups further include aryl groups and substituted aryl groups.
  • the aryl group partially overlaps with the examples of the cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms described above, but is a substituent derived from an aromatic compound, namely a phenyl group, a 1-naphthyl group and a 2-naphthyl group. group, anthracenyl group, phenanthrenyl group, tetracenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group and the like.
  • a phenyl group or a 2-naphthyl group is preferred.
  • aromatic compounds examples include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene.
  • the substituted aryl group partially overlaps with the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, but at least one hydrogen atom of the aryl group is a hydrocarbon group having 1 to 20 carbon atoms,
  • ⁇ Q ⁇ Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand and a neutral ligand capable of coordinating with a lone pair, in the same or different combinations.
  • the halogen atom is exemplified by a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a chlorine atom being preferred.
  • the details of the hydrocarbon group are as described above, and the number of carbon atoms in the hydrocarbon group is preferably 1-7.
  • anionic ligands include alkoxy groups such as methoxy group, t-butoxy group and phenoxy group, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.
  • Neutral ligands capable of coordinating with a lone pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane and the like. Ether compounds and the like can be exemplified.
  • ⁇ j ⁇ j is an integer of 1 to 4, preferably 2;
  • bridged metallocene compound (P) examples include bridged metallocene compounds (P1) in which one or both of R 13 and R 14 in the formula (1) are aryl groups.
  • both R 13 and R 14 are aryl groups, and either one of R 2 and R 3 is a saturated hydrocarbon group having 4 carbon atoms.
  • Certain bridged metallocene compounds (P2) are mentioned.
  • Examples of the bridged metallocene compound (P2) include a bridged metallocene compound in which all of R 1 to R 4 other than the saturated hydrocarbon group having 4 carbon atoms are hydrogen atoms , and A bridged metallocene compound in which two groups adjacent to the saturated hydrocarbon group of Formula 4 are hydrogen atoms, and a non-adjacent group is a methyl group can be mentioned.
  • bridged metallocene compound (P) examples include: [dimethylmethylene ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -fluorenyl)]zirconium dichloride, [dimethylmethylene ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -2,7-di-t-butylfluorenyl )]zirconium dichloride, [dimethylmethylene ( ⁇ 5 -cyclopentadienyl)( ⁇ 5 -3,6-di-t-butylfluorenyl)]zirconium dichloride, [dimethylmethylene ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [dimethylmethylene ( ⁇ 5 -cyclopentadienyl)( ⁇ 5 -tetramethyloctahydrodibenzofluor
  • Examples of the bridged metallocene compound (P) further include a compound in which the zirconium atom of the above compound is replaced by a hafnium atom or a titanium atom, and a compound in which the chloro ligand is replaced by a methyl group.
  • ⁇ 5 -tetramethyloctahydrodibenzofluorenyl which is a constituent part of the exemplified bridged metallocene compound (P), is 4,4,7,7-tetramethyl-(5a,5b,11a,12,12a- ⁇ 5 ) -1,2,3,4,7,8,9,10-octahydrodibenzo[b,H]fluorenyl group
  • ⁇ 5 -octamethyloctahydrodibenzofluorenyl is 1,1,4,4, 7,7,10,10-octamethyl-(5a,5b,11a,12,12a- ⁇ 5 )-1,2,3,4,7,8,9,10-octahydrodibenzo[b,H]fluorenyl each represents a group.
  • the bridged metallocene compound (P) may be used alone or in combination of two or more.
  • the compound (Q) consists of an organometallic compound (Q-1), an organoaluminumoxy compound (Q-2) and a compound (Q-3) that reacts with the bridged metallocene compound (P) to form an ion pair. At least one compound selected from the group.
  • organometallic compound (Q-1) specifically, the following organometallic compounds (Q-1a), (Q-1b), (Q-1c) of Groups 1, 2, 12 or 13 of the periodic table ).
  • Q-1a An organoaluminum compound represented by the general formula R am Al (OR b ) n H p X q .
  • tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum; Tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methyl
  • (Q-1b) A complex alkylate of a Group 1 metal of the periodic table represented by the general formula M 2 AlR a 4 and aluminum.
  • M 2 represents Li, Na or K
  • R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.
  • Examples of such compounds include LiAl(C 2 H 5 ) 4 and LiAl(C 7 H 15 ) 4 .
  • (Q-1c) A dialkyl compound of a Group 2 or Group 12 metal of the periodic table represented by the general formula R a R b M 3 .
  • R a and R b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 is Mg, Zn or Cd.
  • the organoaluminumoxy compound (Q-2) conventionally known aluminoxanes can be used as they are. Specifically, compounds represented by the following general formula [III] and compounds represented by the following general formula [IV] can be mentioned.
  • R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.
  • methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is used.
  • These aluminoxanes may be mixed with a small amount of organoaluminum compounds.
  • a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687 is also applied. be able to.
  • the "benzene-insoluble organoaluminumoxy compound” that may be used in the present invention means that the Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, particularly preferably 5% or less, in terms of Al atoms. It is a compound that is 2% or less and is insoluble or sparingly soluble in benzene.
  • organoaluminumoxy compound (Q-2) examples include modified methylaluminoxane represented by the following general formula [V].
  • R is a hydrocarbon group having 1 to 10 carbon atoms, m and n each independently represent an integer of 2 or more.
  • Methylaluminoxane which is an example of the organoaluminumoxy compound (Q-2), is commonly used as an activator in polyolefin polymerization because it is readily available and has high polymerization activity.
  • methylaluminoxane has been used in solutions of aromatic hydrocarbons such as toluene or benzene, which are environmentally undesirable, because it is difficult to dissolve in saturated hydrocarbons. Therefore, in recent years, a flexible body of methylaluminoxane represented by the formula [V] has been developed and used as an aluminoxane dissolved in a saturated hydrocarbon.
  • This modified methylaluminoxane of formula [V] is prepared using trimethylaluminum and alkylaluminums other than trimethylaluminum, for example, as shown in US Pat. Nos. 4,960,878 and 5,041,584. and prepared using, for example, trimethylaluminum and triisobutylaluminum.
  • Aluminoxanes in which Rx is an isobutyl group are commercially available in the form of saturated hydrocarbon solutions under the trade names of MMAO and TMAO (see Tosoh Finechem Corporation, Tosoh Research & Technology Review, Vol 47, 55 (2003)).
  • organoaluminumoxy compound (Q-2) an organoaluminumoxy compound containing boron represented by the following general formula [VI] can also be mentioned.
  • R c represents a hydrocarbon group having 1 to 10 carbon atoms.
  • R d may be the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Patent Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-5321106. In addition, heteropolycompounds and isopolycompounds may also be mentioned.
  • the ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VII].
  • R e+ includes H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like.
  • R f to R i may be the same or different, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. , preferably a substituted aryl group.
  • carbenium cations include triphenylcarbenium cations, tris(4-methylphenyl)carbenium cations, and trisubstituted carbenium cations such as tris(3,5-dimethylphenyl)carbenium cations. .
  • ammonium cation examples include trialkyl-substituted ammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation.
  • N,N-dialkylanilinium cations such as N,N-dimethylanilinium cations, N,N-diethylanilinium cations, N,N-2,4,6-pentamethylanilinium cations, diisopropylammonium cations, and dialkylammonium cations such as dicyclohexylammonium cations.
  • phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cations, tris(4-methylphenyl)phosphonium cations, and tris(3,5-dimethylphenyl)phosphonium cations.
  • R e+ is preferably a carbenium cation or an ammonium cation, and particularly preferably a triphenylcarbenium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation.
  • compounds containing carbenium cations include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis ⁇ 3, 5-di-(trifluoromethyl)phenyl ⁇ borate, tris(4-methylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, tris(3,5-dimethylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, etc. can be exemplified.
  • compounds containing trialkyl-substituted ammonium cations include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, and trimethylammonium.
  • compounds containing N,N-dialkylanilinium cations include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl ) borate, N,N-dimethylanilinium tetrakis ⁇ 3,5-di(trifluoromethyl)phenyl ⁇ borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl) Borate, N,N-diethylanilinium tetrakis ⁇ 3,5-di(trifluoromethyl)phenyl ⁇ borate, N,N-2,4,6-pentamethylanilinium tetraphenylborate, N,N-2,4 , 6-pentamethylanilinium
  • di-n-propylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate and the like can be exemplified as compounds containing dialkylammonium cations.
  • ionic compounds exemplified in JP-A-2004-51676 can also be used without limitation.
  • the above ionic compound (Q-3) may be used alone or in combination of two or more.
  • Examples of the configuration of the catalyst system include the following [1] to [4]. [1] Containing bridged metallocene compound (P) and compound (Q-2) [2] Containing bridged metallocene compound (P), compound (Q-1) and compound (Q-2) [3] Bridged metallocene compound ( P), including compound (Q-1) and compound (Q-3) [4] bridged metallocene compound (P), compound (Q-2) and compound (Q-3) including bridged metallocene compound (P), Compounds (Q-1) to (Q-3) may be introduced into the reaction system in any order.
  • the olefin polymerization catalyst containing the bridged metallocene compound (P) and the compound (Q) may further contain a carrier (R).
  • the carrier (R) that may be used in the present invention is an inorganic or organic compound, and is a granular or particulate solid. Among these inorganic compounds, porous oxides, inorganic chlorides, clays, clay minerals, and ion-exchange layered compounds are preferred.
  • porous oxides include SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 and the like, or composites or mixtures containing these, such as Using natural or synthetic zeolite, SiO2 - MgO, SiO2 - Al2O3 , SiO2 - TiO2 , SiO2 - V2O5 , SiO2 - Cr2O3 , SiO2 - TiO2 - MgO , etc. can do. Among these, those containing SiO 2 and/or Al 2 O 3 as main components are preferred. The properties of such porous oxides vary depending on the type and production method.
  • a carrier is in the range of 50-1000 m 2 /g, preferably 100-700 m 2 /g, and the pore volume is in the range of 0.3-3.0 cm 3 /g.
  • Such a carrier is used after being calcined at 100 to 1000° C., preferably 150 to 700° C., if necessary.
  • inorganic chlorides MgCl 2 , MgBr 2 , MnCl 2 , MnBr 2 and the like are used.
  • the inorganic chloride may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic chloride in a solvent such as alcohol, the inorganic chloride may be precipitated in the form of fine particles using a precipitating agent.
  • Clay is usually composed mainly of clay minerals.
  • An ion-exchangeable layered compound is a compound having a crystal structure in which planes are stacked in parallel with a weak bonding force due to ionic bonds or the like, and the ions contained therein can be exchanged.
  • Most clay minerals are ion exchange layered compounds.
  • these clays, clay minerals, and ion-exchangeable layered compounds not only naturally occurring ones but also artificially synthesized ones can be used.
  • Clays, clay minerals, and ionic crystalline compounds having layered crystal structures such as hexagonal close-packing type, antimony type, CdCl2 type, and CdI2 type are used as clays, clay minerals, or ion-exchangeable layered compounds.
  • Such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, and dickite.
  • the ion-exchangeable layered compounds include ⁇ -Zr(HAsO 4 ) 2.H 2 O, ⁇ -Zr(HPO 4 ) 2 , ⁇ -Zr(KPO 4 ) 2.3H 2 O, ⁇ -Ti( HPO4 ) 2 , ⁇ -Ti( HAsO4 )2.H2O, ⁇ -Sn( HPO4 ) 2.H2O , ⁇ -Zr( HPO4 ) 2 , ⁇ - Ti ( HPO4 ) 2 and crystalline acid salts of polyvalent metals such as ⁇ -Ti(NH 4 PO 4 ) 2 ⁇ H 2 O and the like.
  • any chemical treatment can be used, such as a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like.
  • Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment.
  • the ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion-exchangeability.
  • Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars.
  • the introduction of another substance (guest compound) between the layers of a layered compound is called intercalation.
  • Guest compounds include cationic inorganic compounds such as TiCl 4 and ZrCl 4 , metal alkoxides such as Ti(OR) 4 , Zr(OR) 4 , PO(OR) 3 and B(OR) 3 (R is a hydrocarbon groups), [ Al13O4 ( OH) 24 ] 7+ , [ Zr4 (OH) 14 ] 2+ , [ Fe3O ( OCOCH3 ) 6 ] + , metal hydroxide ions such as . These compounds are used singly or in combination of two or more.
  • metal alkoxides such as Si(OR) 4 , Al(OR) 3 and Ge(OR) 4 are hydrolyzed and polycondensed.
  • the obtained polymer a colloidal inorganic compound such as SiO 2 , etc. can be coexistent.
  • pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating.
  • clays or clay minerals preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
  • organic compound as the carrier (R) include granular or particulate solids having a particle size in the range of 0.5 to 300 ⁇ m.
  • (co)polymers produced mainly from ⁇ -olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, and styrene can be exemplified as a (co)polymer produced as a main component, and a modified product thereof.
  • each component of the polymerization catalyst can be selected arbitrarily. At least two or more of each component in the catalyst may be contacted in advance.
  • the bridged metallocene compound (P) (hereinafter also referred to as “component (P)”) is generally used in an amount of 1 ⁇ 10 ⁇ 9 to 1 ⁇ 10 ⁇ 1 mol, preferably 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 1 mol, per liter of reaction volume. It is used in such an amount that it becomes 10 -2 mol.
  • the organometallic compound (Q-1) (hereinafter also referred to as “component (Q-1)”) has a molar ratio [( Q-1)/M] is generally 0.01 to 50,000, preferably 0.05 to 10,000.
  • the organoaluminumoxy compound (Q-2) (hereinafter also referred to as “component (Q-2)”) is composed of the aluminum atom in component (Q-2) and the transition metal atom (M) in component (P). is used in an amount such that the molar ratio [(Q-2)/M] of is usually 10 to 5,000, preferably 20 to 2,000.
  • the ionic compound (Q-3) (hereinafter also referred to as "component (Q-3)”) has a molar ratio [( Q-3)/M] is usually used in an amount of 1 to 10,000, preferably 1 to 5,000.
  • the polymerization temperature is usually -50°C to 300°C, preferably 30°C to 250°C, more preferably 100°C to 250°C, still more preferably 130°C to 200°C. In the polymerization temperature range within the above range, the higher the temperature, the lower the viscosity of the solution during polymerization, making it easier to remove the heat of polymerization.
  • the polymerization pressure is usually normal pressure to 10 MPa gauge pressure (MPa-G), preferably normal pressure to 8 MPa-G.
  • the polymerization reaction can be carried out in any of a batch system, a semi-continuous system and a continuous system. Furthermore, it is also possible to carry out the polymerization continuously in two or more polymerization vessels having different reaction conditions.
  • the molecular weight of the obtained copolymer can be adjusted by changing the hydrogen concentration in the polymerization system and the polymerization temperature. Furthermore, it can also be adjusted by the amount of the compound (Q) used. When hydrogen is added, the appropriate amount thereof is about 0.001 to 5,000 NL per 1 kg of copolymer produced.
  • the polymerization solvent used in the liquid phase polymerization method is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50°C to 200°C under normal pressure.
  • the polymerization solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. and particularly preferably hexane, heptane, octane, decane, and cyclohexane.
  • the ⁇ -olefin to be polymerized itself can also be used as a polymerization solvent.
  • Aromatic hydrocarbons such as benzene, toluene, and xylene and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane can also be used as polymerization solvents. From the viewpoint of minimizing the impact of
  • the ethylene/ ⁇ -olefin copolymer (Y) may be graft-modified with some polar group, but is preferably not graft-modified.
  • vinyl compounds having a polar group used for graft modification include vinyl compounds having oxygen-containing groups such as acids, acid anhydrides, esters, alcohols, epoxies, and ethers, and nitrogen-containing groups such as isocyanates and amides.
  • vinyl compounds and vinyl compounds having a silicon-containing group such as vinylsilane.
  • vinyl compounds having an oxygen-containing group are preferred, and more specifically, unsaturated epoxy monomers, unsaturated carboxylic acids and their derivatives are more preferred, and unsaturated dicarboxylic acids and their acid anhydrides are more preferred. , maleic acid, nadic acid TM and their anhydrides are particularly preferred. Graft modification can be performed by a conventionally known method.
  • the content of the ethylene/ ⁇ -olefin copolymer (Y) in the resin composition of the present invention is preferably 0.001 to 20 parts by mass, more preferably 0, per 100 parts by mass of the resin (X). 0.002 to 15 parts by weight, more preferably 0.005 to 10 parts by weight, even more preferably 0.01 to 5 parts by weight, and particularly preferably 0.1 to 3 parts by weight.
  • the content of the ethylene/ ⁇ -olefin copolymer (Y) is at least the lower limit, the antifoaming properties (foam suppressing property and foam breaking property) of the ethylene/ ⁇ -olefin copolymer (Y) are sufficiently demonstrated.
  • the content is equal to or less than the upper limit, the ethylene/ ⁇ -olefin copolymer (Y) is less likely to bleed out from the resin composition of the present invention and its cured product.
  • the resin composition of the present invention contains, in addition to the resin (X) and the ethylene/ ⁇ -olefin copolymer (Y), a catalyst (curing agent), a solvent, a plasticizer, and a filler (filler) as necessary. , colorants, additives, and the like.
  • the "additional component" is preferably included in the B liquid.
  • the resin composition of the present invention contains a catalyst, that is, a curing catalyst, for the purpose of accelerating the curing of the curable resin (X1). can be contained.
  • the catalyst is not particularly limited, but includes liquid catalysts and solid catalysts at room temperature. A catalyst that is liquid at room temperature is preferred, and a room temperature curing type catalyst is more preferred. A liquid catalyst may be used in combination with a solid catalyst as long as the effects of the present invention are not impaired.
  • catalysts include amine compounds such as aliphatic polyamines, alicyclic polyamines, polyamide polyamines, and polymercaptans, modified compounds thereof, and compounds such as tin, bismuth, lead, nickel, and cobalt.
  • amine compounds such as aliphatic polyamines, alicyclic polyamines, polyamide polyamines, and polymercaptans, modified compounds thereof, and compounds such as tin, bismuth, lead, nickel, and cobalt.
  • a single species may be used, or two or more species may be mixed and used.
  • catalysts include triethylamine, tripropylamine, N-methylmorpholine, triethanolamine, triethylenediamine, 1,1′-dichloro-4,4′-diaminodiphenylmethane, 1,1′,2,2′- tetrachloro-4,4'-diaminodiphenylmethane, di(methylthio)toluenediamine, dimorpholinodiethylene glycol, tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth octoate, bismuth neodecanoate, lead octylate, lead naphthenate, nickel naphthenate, cobalt octylate and the like.
  • the reactivity of the curable resin composition can be controlled.
  • the dry-to-touch time specified in JIS K5400 is preferably 2 to 3600 seconds, more preferably 2 to 1800 seconds.
  • solvent examples include, but are not limited to, aromatic hydrocarbons such as xylene, toluene and ethylbenzene; aliphatic hydrocarbons such as hexane, heptane, octane and decane; and alicyclic hydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane.
  • aromatic hydrocarbons such as xylene, toluene and ethylbenzene
  • aliphatic hydrocarbons such as hexane, heptane, octane and decane
  • alicyclic hydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane.
  • aromatic hydrocarbons can be preferably used.
  • plasticizer examples include, but are not limited to, dibutyl phthalate (abbreviation: DBP), dioctyl phthalate (also known as bis-2-ethylhexyl phthalate, abbreviations: DEHP, DOP, DEHA), diisononyl phthalate (abbreviation: DINP), esters of phthalic anhydride and alcohol, dioctyl adipate (also known as bis-2-ethylhexyl adipate, abbreviations: DEHA, DOA) and other esters of adipic acid and alcohol, tricresyl phosphate, trioctyl phosphate, epoxidation Soybean oil, denatured castor oil.
  • DBP dibutyl phthalate
  • DEHP dioctyl phthalate
  • DEHA diisononyl phthalate
  • DEHA diisononyl phthalate
  • DEHA dioctyl adipate
  • phthalic acid-based plasticizers are less likely to cause bleeding out and can be preferably used.
  • the content of the plasticizer in the resin composition of the present invention is 100 parts by mass or less, preferably 1 to 80 parts by mass, more preferably about 5 to 50 parts by mass with respect to 100 parts by mass of the resin (X). desirable.
  • the content in the entire resin composition is 50% by mass or less, preferably 1 to 40% by mass, more preferably 1 to 30% by mass.
  • filler inorganic fillers are preferable, powder fillers such as mica, carbon black, silica, calcium carbonate, talc, graphite, stainless steel, aluminum, aluminum hydroxide, calcium sulfate, barium sulfate, and zinc oxide; glass fiber and fibrous fillers such as metal fibers.
  • the content of the filler in the resin composition of the present invention is 150 parts by mass or less, preferably 10 to 120 parts by mass, more preferably about 30 to 100 parts by mass with respect to 100 parts by mass of the resin (X). desirable.
  • the content in the entire resin composition is 60 mass % or less, preferably 10 to 55 mass %, preferably 20 to 50 mass %.
  • coloring agent examples include, but are not limited to, titanium dioxide, carbon black, red iron oxide, chromium oxide, ultramarine, phthalocyanine green, and phthalocyanine blue.
  • additives examples include conventionally known antifoaming agents, leveling agents, anti-separation agents, stabilizers, silane coupling agents, organic compounds and inorganic compounds that do not correspond to the ethylene/ ⁇ -olefin copolymer (Y).
  • lubricants include conventionally known antifoaming agents, leveling agents, anti-separation agents, stabilizers, silane coupling agents, organic compounds and inorganic compounds that do not correspond to the ethylene/ ⁇ -olefin copolymer (Y).
  • lubricants light stabilizers, antioxidants, phosphorus processing heat stabilizers, antistatic agents, and the like.
  • antioxidants and light stabilizers are preferably added as appropriate depending on the subsequent use of the composition.
  • Other resins, elastomers, etc. may be added as long as the object of the present invention is not impaired.
  • antioxidants examples include, for example, trade names of Irganox 1010, 1076, 1135, 245, 3114, and 3790 manufactured by Ciba Specialty Chemicals; -60, AO-70, AO-80 and the like.
  • an antioxidant is added, it is preferably added in an amount of 0.05 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the resin (X).
  • Examples of the phosphorus-based processing heat stabilizer include, for example, trade names of Irgafos 38, 126, P-EPQ, etc. manufactured by Ciba Specialty Chemicals; 11C, 24, 36 and the like.
  • the phosphorus-based processing heat stabilizer is added, it is preferably added in the range of 0.05 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the resin (X).
  • Examples of the light stabilizer include, for example, the trade names of Tinuvin P, 234, 326, 327, 328, 329, 213, 571, 1577, and 622LD manufactured by Ciba Specialty Chemicals; Same 144, Same 765, Same 770, Same B75, Same B88, etc. Sanol LS-770, Same 765, Same 2626, Same 944, etc., Asahi Denka Kogyo's product name: LA- No. 32, No. 36, No. 1413, No. 52, No. 62, No. 77, No. 601, No. T-940 and other ultraviolet absorbers or hindered amine light stabilizers.
  • an ultraviolet absorber and a hindered amine light stabilizer in combination. It is preferable to add in the following range.
  • organic compound-based lubricant examples include fatty acid amides.
  • Commercially available products include Nikka Amide, Bis Amide, Slipax, etc. manufactured by Nippon Kasei Co., Ltd., or Clariant. Trade name: Ricowax, trade name: Ricolb, etc. manufactured by the company.
  • examples of the inorganic compound lubricant include talc and silica.
  • an organic compound-based lubricant is added in the present invention, it is preferably added in a range of 0.05 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the resin (X).
  • Conventionally known antifoaming agents that do not correspond to the ethylene/ ⁇ -olefin copolymer (Y) include ethylene/ ⁇ -olefin copolymers, silicone-based, acrylic-based, butadiene-based, and the like.
  • the resin composition of the present invention can be obtained by mixing the resin (X), the ethylene/ ⁇ -olefin copolymer (Y), and optionally the additional component by a known method.
  • the resin composition of the present invention is produced by the resin (X) (excluding the copolymer (Y') described later) and the following method ( ⁇ ), and the requirements (y-1) and (y-2), or the step of mixing the ethylene/ ⁇ -olefin copolymer (Y') satisfying the requirements (y-2) and (y-4), and optionally the additional components. It can be manufactured by a method.
  • Method ( ⁇ ) A method comprising a step of solution polymerizing an ⁇ -olefin in the presence of a catalyst system containing the bridged metallocene compound (P) represented by the formula (1) and the compound (Q) Resin (X) is the curable resin (X1), the resin (X) is added to the composition containing all the constituents other than the resin (X) immediately before curing the resin composition of the present invention. may be mixed with other ingredients in a previous step.
  • the curable resin (X1) may be formed in the process of preparing the resin composition of the present invention by, for example, mixing a liquid A containing an organic polyisocyanate and a liquid B containing an active hydrogen group-containing compound.
  • the ethylene/ ⁇ -olefin copolymer (Y) is added to the ethylene/ ⁇ - It may be added to the composition containing all the constituents other than the olefin copolymer (Y), and may be mixed with other components in a previous step.
  • the ethylene/ ⁇ -olefin copolymer (Y) is added to the B liquid before mixing the A and B liquids. Mixing is preferred.
  • the resin (X) is a curable resin (X1)
  • the above “additional components” such as the catalyst (curing agent), solvent, plasticizer, filler, colorant, additive, etc. It may be added to the resin composition just before it is to be cured, or it may be mixed with the other ingredients in a previous step. In addition, some components of the "additional components” are mixed with other components in the process of manufacturing the resin composition, and then the “additional components” are mixed immediately before curing the resin composition. may be added to the resin composition.
  • the "additional component" is preferably mixed with the B liquid before mixing the A and B liquids. .
  • the resin composition of the present invention comprises the active hydrogen group-containing compound and the optionally used " It can be obtained by mixing the liquid B containing the "additional component", the liquid A containing the organic polyisocyanate, and the ethylene/ ⁇ -olefin copolymer (Y).
  • a curable resin composition containing the curable resin (X) and the ethylene/ ⁇ -olefin copolymer (Y) is formed through the reaction of the liquids A and B by this mixing.
  • the resin composition of the present invention comprises the above active hydrogen group-containing compound, the above ethylene/ ⁇ -olefin copolymer (Y), and optionally the above "other constituent components" B It can also be obtained by mixing the liquid and the A liquid containing the organic polyisocyanate. Also in this case, the resin composition containing the curable resin (X1) and the ethylene/ ⁇ -olefin copolymer (Y) is similarly formed through the reaction of the liquids A and B by mixing. Become.
  • the conditions for curing the resin composition of the present invention may be normal temperature curing or heat curing.
  • the means for producing the cured product is not limited, and known techniques can be used.
  • a cured product having a desired shape can be obtained by coating or casting the resin composition of the present invention and curing it as it is. That is, the present invention also provides a molded article formed from the resin composition of the present invention.
  • the resin composition of the present invention has remarkably good antifoaming properties, especially antifoaming properties. Therefore, when the resin (X) is the curable resin (X1), when the resin composition of the present invention is used to form a cast product, the curable resin composition Alternatively, bubbles and gas inside the curing reaction intermediate produced from the curable resin composition are degassed, and a molded body having excellent smoothness and excellent mechanical properties can be obtained without impairing the gloss of the surface. In addition, when used as a coating agent, not only does it leave no air bubbles inside the coating film, but it also provides a coating film surface that is rich in smoothness without impairing the gloss of the surface, and that has excellent mechanical properties and excellent finishing properties. That is, the present invention also provides a paint containing the resin composition of the present invention, and also provides a coating film formed from the resin composition.
  • Molded products formed from the resin composition of the present invention include industrial products as thermosetting molded products, or paints as coating agents, industrial products as room temperature curable molded products, injection products, or coatings as coating agents. It can be used as a coating material such as a coating film waterproofing material and a flooring material. That is, the present invention also provides a waterproof material formed from the resin composition of the present invention. Furthermore, the present invention also provides an adhesive formed from the resin composition of the present invention.
  • the solubility parameter can be calculated based on D.W. Van Krevelen's estimation method. Specifically, the solubility parameter ((MPa) 1/2 ) was obtained based on the cohesive energy and molar molecular volume.
  • the weight average molecular weight (Mw) was determined using the following high-speed GPC measurement device and measurement conditions.
  • High-speed GPC measurement device HLC8320GPC manufactured by Tosoh Corporation
  • Mobile phase THF (manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free, grade for liquid chromatography)
  • Column Two TSKgel Super Multipore HZ-M manufactured by Tosoh Corporation were connected in series.
  • Sample concentration 5 mg/mL
  • Mobile phase flow rate 0.35 mL/min
  • Measurement temperature 40°C Standard sample for calibration curve: PStQuick MP-M manufactured by Tosoh Corporation
  • Ethylene content was measured using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of ortho-dichlorobenzene/heavy benzene (80/20% by volume) as a solvent, a sample concentration of 55 mg/0.6 mL, and a measurement temperature of 120. °C, 13 C (125 MHz) as the observation nucleus, single pulse proton decoupling as the sequence, 4.7 ⁇ s (45° pulse) as the pulse width, 5.5 seconds as the repetition time, 10,000 times or more as the number of integrations, chemical Measured using 27.50 ppm as a shift reference.
  • the ethylene content was determined from the 13 C-NMR spectrum according to "Polymer Analysis Handbook" (published by Asakura Shoten, pp. 163-170), G.I. J. Ray (Macromolecules, 10, 773 (1977)); C. Randall (Macro-molecules, 15, 353 (1982)); It was obtained based on the report by Kimura (Polymer, 25, 4418 (1984)) et al.
  • MMAO-3A modified methylaluminoxane manufactured by Tosoh Finechem Co., Ltd., hereinafter referred to as "MMAO"
  • MMAO-3A modified methylaluminoxane
  • 0.2 mmol of triisobutylaluminum was charged into the polymerization vessel, and then 0.192 mmol of MMAO in terms of aluminum atom and [methylphenylmethylene ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -2,7-di- t-Butylfluorenyl)]zirconium dichloride (0.0006 mmol) and toluene were mixed in advance for 15 minutes or more, and the resulting mixture was charged into a polymerization vessel to initiate polymerization. After that, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130° C. for 15 minutes.
  • 0.2 mmol of triisobutylaluminum was charged into the polymerization vessel, and then 0.115 mmol of MMAO in terms of aluminum atom and [methylphenylmethylene ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -2,7-di- t-Butylfluorenyl)]zirconium dichloride (0.0004 mmol) and toluene were mixed in advance for 15 minutes or more, and the resulting mixture was charged into a polymerization vessel to initiate polymerization. After that, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130° C. for 15 minutes.
  • Example 1 (A liquid) As liquid A, an isocyanate-containing prepolymer (Hiprene P-306A manufactured by Mitsui Chemicals, Inc.; viscosity 6,000 cps/25° C.) was used. Here, the NCO group content in this isocyanate-containing prepolymer is 0.69 milliequivalents (2.9% by weight).
  • the MC-506 used as the polyether polyol was specifically composed of 3,3′-dichloro-4,4′-diaminodiphenylmethane: 24% by weight and aniline and 2-chloro in the presence of a mineral acid.
  • a liquid amine comprising 24% by weight of an aromatic polyamine obtained by condensing aniline with formaldehyde and 52% by weight of a polyether polyol, and has an active hydrogen content of 3.7 milliequivalents.
  • the ratio of the number of active hydrogen groups in the active hydrogen group-containing compound to one isocyanate group in the isocyanate-containing prepolymer was 0.9 ( ⁇ (3. 7 ⁇ 8.8)/(0.69 ⁇ 51.5)).
  • Example 2 A curable resin composition was obtained in the same manner as in Example 1, except that the antifoaming agent was changed to the ethylene/ ⁇ -olefin copolymer (Y-2).
  • Example 3 A curable resin composition was obtained in the same manner as in Example 1, except that the antifoaming agent was changed to the ethylene/ ⁇ -olefin copolymer (Y-3).
  • Example 1 A curable resin composition was obtained in the same manner as in Example 1, except that the antifoaming agent was changed to the ethylene/ ⁇ -olefin copolymer (Y-4).
  • Example 2 A curable resin composition was obtained in the same manner as in Example 1, except that the antifoaming agent was changed to the ethylene/ ⁇ -olefin copolymer (Y-5).
  • Example 3 A curable resin composition was obtained in the same manner as in Example 1, except that the antifoaming agent was changed to paraffin-based process oil (Z-1).
  • Table 2 shows the amount of each component in Examples and Comparative Examples.
  • Table 3 shows the evaluation results of the curable resin compositions obtained in Examples and Comparative Examples.

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JP7532700B1 (ja) 2024-05-22 2024-08-13 シーカ テクノロジー アクチェンゲゼルシャフト ２剤型ポリウレタン組成物の発泡防止方法及び２剤型ポリウレタン組成物
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