WO2020213746A1 - Corps moulé en résine - Google Patents

Corps moulé en résine Download PDF

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Publication number
WO2020213746A1
WO2020213746A1 PCT/JP2020/017111 JP2020017111W WO2020213746A1 WO 2020213746 A1 WO2020213746 A1 WO 2020213746A1 JP 2020017111 W JP2020017111 W JP 2020017111W WO 2020213746 A1 WO2020213746 A1 WO 2020213746A1
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WIPO (PCT)
Prior art keywords
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resin
mass
resin molded
molded product
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PCT/JP2020/017111
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English (en)
Japanese (ja)
Inventor
大地 樋口
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Dic株式会社
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Priority to JP2021504476A priority Critical patent/JP6927453B2/ja
Publication of WO2020213746A1 publication Critical patent/WO2020213746A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N19/00—Investigating materials by mechanical methods
    • G01N19/02—Measuring coefficient of friction between materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N3/08—Investigating strength properties of solid materials by application of mechanical stress by applying steady tensile or compressive forces

Definitions

  • the present invention relates to a resin molded product.
  • the present application claims priority based on Japanese Patent Application No. 2019-080003 filed in Japan on April 19, 2019, the contents of which are incorporated herein by reference.
  • Resin molded products have excellent flexibility, elasticity, etc., and are used in various applications such as automobile parts, home appliance parts, packaging materials, leather-like sheets, and printing rolls.
  • a urethane resin composition As such a urethane resin composition, a polyol having no aromatic ring and a polyisocyanate having an aromatic ring are reacted to produce a urethane prepolymer having an isocyanate group terminal, and the urethane prepolymer is reacted with a branched diol to form a main agent.
  • a urethane resin composition containing a curing agent has been proposed (see, for example, Patent Document 1).
  • the 100% modulus measured by the following method is 5 MPa or less, and the hysteresis loss at the time of 100% elongation recovery measured by the following method is 20% or less, and the following The dynamic friction force measured by the above method is 2 kN or less.
  • the loss ratio of the amount of heat obtained from the difference between the amount of heat given when the test piece is pulled and the amount of heat released when the test piece is pulled back from the integrated value of the graph of the applied load and the amount of deformation is defined as the hysteresis loss.
  • the resin molded product of the present invention can have both flexibility and scratch resistance.
  • the 100% modulus of the resin molded product measured by the following method is 5 MPa or less.
  • the 100% modulus is preferably 4.5 MPa or less, more preferably 4.0 MPa or less, still more preferably 2.0 MPa or more, and for example, 2.5 MPa or more and 3.0 MPa or more.
  • the resin molded product has a hysteresis loss of 20% or less at the time of 100% elongation recovery measured by the following method.
  • the hysteresis loss is preferably 10% or less, more preferably 5% or less, still more preferably 1% or less, and the lower limit is preferably 0%, for example, 5% or more, or even 10% or more. Permissible.
  • the loss ratio of the amount of heat obtained from the difference between the amount of heat given when the test piece is pulled and the amount of heat released when the test piece is pulled back from the integrated value of the graph of the applied load and the amount of deformation is defined as the hysteresis loss.
  • the resin molded body has a dynamic friction force of 2 kN or less measured by the following method.
  • the dynamic friction force is preferably 1 kN or less, more preferably 0.5 kN or less, still more preferably 0.1 kN or less, and for example, 0.1 kN or more, and even 0.5 kN or more is allowed.
  • the thickness of the resin molded product is preferably 1 ⁇ m or more, preferably 3 ⁇ m or more, further preferably 5 ⁇ m or more, preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less.
  • the 100% modulus and the hysteresis loss are, for example, the ratio of the rigid portion and the flexible portion in the molecular chain of the resin contained in the resin molded product, the rigidity, the degree of flexibility, the degree of cross-linking, and the like. It can be achieved by adjusting.
  • the resin preferably has a flexible portion (soft segment), and when the flexible portion has a glass transition temperature, the glass transition temperature is determined. For example, it is 20 ° C. or lower, preferably 0 ° C. or lower, ⁇ 5 ° C. or lower, ⁇ 15 ° C. or lower, ⁇ 25 ° C. or lower, ⁇ 35 ° C. or lower.
  • the resin preferably has a rigid portion (hard segment).
  • the rigid site (hard segment) is a site that physically or chemically crosslinks the soft segment, and the physical crosslink includes a functional group (urethane bond group, urea bond group, etc.) capable of forming a hydrogen bond.
  • Chemical cross-linking includes cross-linking with a cross-linking agent (polyfunctional monomer, sulfide agent, etc.). Chemical cross-linking can be reversibly formed, while physical cross-linking can be carried out. As the amount of deformation increases, it is irreversibly divided and the hysteresis loss tends to increase. Therefore, the rigid portion has a higher proportion of cross-linking by chemical cross-linking than physical cross-linking. It is more preferable as a method for reducing the loss.
  • the resin may be a silicone resin, an acrylic resin, or a urethane resin. Among them, the resin preferably contains a urethane resin.
  • the urethane resin is preferably a reaction product of the main agent (i) containing the polymer (A) having a hydroxyl group and the curing agent (ii).
  • the main agent (i) and the curing agent (ii) may each contain components other than the components directly involved in the formation of the cured product (for example, polymers, compounds having a curing action, etc.), and the main agent (i)
  • the composition of i) and the composition of the curing agent (ii) may be used.
  • the polymer (A) having a hydroxyl group is preferably a polyol (a) or a reaction product of the polyol (a) and the polyisocyanate (b).
  • the polyol (a) contains a polycarbonate polyol (a1) that is liquid at 25 ° C. (hereinafter, may be referred to as "liquid polycarbonate polyol (a1)").
  • liquid polycarbonate polyol (a1) examples include an esterification reaction product of a carbonic acid ester and a polyhydric alcohol, and a reaction product of a polyhydric alcohol and a phosgene, which is liquid at 25 ° C.
  • an aliphatic carbonate an alicyclic carbonate (hereinafter, including an alicyclic structure may be referred to as an "alicyclic”).
  • aromatic carbonates hereinafter, the inclusion of aromatic structures may be collectively referred to as "aromatic”
  • the aliphatic carbonate include saturated aliphatic carbonates such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate and ethylisobutyl carbonate; ethylene carbonate, trimethylene carbonate, etc.
  • Tetramethylene carbonate 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1, Examples thereof include unsaturated aliphatic carbonates such as 4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate and 2,4-pentylene carbonate.
  • the aromatic carbonate include diphenyl carbonate and dibenzyl carbonate.
  • polyhydric alcohol one kind or two or more kinds can be used, for example, ethylene glycol, propylene glycol, butanediol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, diethylene glycol, di.
  • Linear or branched diols such as propylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A; trimethylolmethane , Trimethylol propane, ditrimethylol propane, pentaerythritol, dipentaerythritol and other trifunctional or higher functional polyols.
  • the liquid polycarbonate polyol may be liquid at 25 ° C., may be an amorphous or crystalline polycarbonate polyol, and is preferably an amorphous polycarbonate polyol.
  • the number of hydroxyl groups contained in the liquid polycarbonate polyol is preferably 2.
  • the viscosity of the liquid polycarbonate polyol is preferably 10,000 mPa ⁇ s or less, more preferably 7,000 mPa ⁇ s or less, still more preferably 5,000 mPa ⁇ s or less, for example 100 mPa ⁇ s, at room temperature (25 ° C.). As mentioned above, it is preferably 500 mPa ⁇ s or more.
  • the number average molecular weight of the liquid polycarbonate polyol is preferably more than 500, more preferably 600 or more, still more preferably 700 or more, preferably less than 2,000, more preferably 1800 or less, still more preferably 1,500. It is as follows.
  • the number average molecular weight and the weight average molecular weight represent conversion values obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.
  • the glass transition temperature of the liquid polycarbonate polyol is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 90 ° C. or higher, further preferably ⁇ 80 ° C. or higher, particularly preferably ⁇ 75 ° C. or higher, and preferably ⁇ 5 ° C. or lower. It is more preferably ⁇ 15 ° C. or lower, further preferably ⁇ 25 ° C. or lower, and particularly preferably ⁇ 35 ° C. or lower.
  • the content of the liquid polycarbonate polyol is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and the upper limit is 100% by mass in the polyol (a).
  • the polyol (a) may contain other polyols (a2) in addition to the polycarbonate polyol (a1) which is liquid at 25 ° C.
  • examples of the other polyol (a2) include polyester polyols, polyether polyols, polycarbonate polyols other than the liquid polycarbonate polyol (a1), low molecular weight polyols, and the like.
  • polyester polyol one kind or two or more kinds can be used.
  • a polyester polyol obtained by reacting a low molecular weight polyol with a polycarboxylic acid; a cyclic ester compound such as ⁇ -caprolactone is ring-opened.
  • Polyester polyols obtained by polymerization reaction; polyester polyols obtained by copolymerizing these compounds and the like can be mentioned.
  • the low molecular weight polyol used for producing the polyester polyol one kind or two or more kinds can be used, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1 , 3-Propanediol, Dipropylene glycol, Tripropylene glycol, 1,2-Butandiol, 1,3-Butandiol, 1,4-Butandiol, 2,3-Butandiol, 1,5-Pentanediol, Neo Pentyl glycol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Diol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl
  • polystyrene resin is 50.
  • examples thereof include aliphatic polyols having a temperature of 300 or more; polyols having an alicyclic structure such as cyclohexanedimethanol and hydrogenated bisphenol A; polyols having an aromatic structure such as bisphenol A and bisphenol F.
  • polycarboxylic acid one kind or two or more kinds can be used, for example, an aliphatic polycarboxylic acid such as succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid; 1,4-cyclohexanedicarboxylic acid, cyclohexane.
  • Alicyclic polycarboxylic acids such as tricarboxylic acids; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; anhydrides or esterified products thereof.
  • the polyether polyol one kind or two or more kinds can be used.
  • the compound having two or more active hydrogen atoms include propylene glycol, trimethylolglycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, and di.
  • the alkylene oxide include propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.
  • polycarbonate polyol other than the liquid polycarbonate polyol (a1) examples include a polycarbonate polyol that is solid at 25 ° C.
  • the number average molecular weight of the polyester polyol, the polyether polyol, and the polycarbonate polyol other than the polycarbonate polyol (a1) is preferably more than 300, more preferably 500 or more, still more preferably 700 or more, and preferably 10,000 or less. , More preferably 5,000 or less, still more preferably 4,000 or less.
  • the low molecular weight polyol one kind or two or more kinds can be used, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene.
  • Glycol tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,5-hexane Diol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol , 1,12-Dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2 An aliphatic polyol having a
  • the content of the other polyol is, for example, 30% by mass or less, 20% by mass or less, 10% by mass or less, and the lower limit is 0% by mass in the polyol (a).
  • polyisocyanate (b) one kind or two or more kinds can be used, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aliphatic or alicyclic polyisocyanates. It is preferable to use it.
  • aliphatic or alicyclic polyisocyanate one type or two or more types can be used, for example, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3.
  • -Cyclopentylene diisocyanate 1,3-cyclohexamethylene diisocyanate, 1,4-cycloheximethylene diisocyanate, 1,3-di (isocyanate methyl) cyclohexane, 1,4-di (isocyanate methyl) cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate and the like can be used.
  • an allophanate-modified product or an isocyanurate-modified product of the aliphatic or alicyclic polyisocyanate can be used.
  • an allophanate modified or isocyanurate modified product of an aliphatic or alicyclic polyisocyanate is preferable, an isocyanurate modified product of an aliphatic or alicyclic polyisocyanate is more preferable, and an isocyanurate modified product of an aliphatic polyisocyanate is more preferable. Is even more preferable.
  • the molar ratio (NCO / OH) of the isocyanate group contained in the polyisocyanate (b) to the hydroxyl group contained in the polyol (a) is preferably 0.8 or more, more preferably 0.9 or more, still more preferably 0.9 or more. It is 1.0 or more, preferably 1.3 or less, more preferably 1.2 or less, and further preferably 1.1 or less.
  • the polymer (A) may be the polyol (a) as it is, or may be produced by reacting the polyol (a) with the polyisocyanate (b).
  • a urethanization catalyst When reacting the polyol (a) and the polyisocyanate (b), a urethanization catalyst may coexist, if necessary.
  • the urethanization catalyst one kind or two or more kinds can be used, and for example, a nitrogen-containing compound such as triethylamine, tributylamine, benzyldibutylamine, triethylenediamine, N-methylmorpholin; or titanium tetrabutoxide, dibutyltin oxide.
  • Organic metal compounds; or inorganic compounds such as iron chloride and zinc chloride.
  • a reaction solvent may coexist during the reaction.
  • the reaction solvent one kind or two or more kinds can be used, for example, an aromatic hydrocarbon solvent such as toluene and xylene; a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone and acetylacetone; and an ether solvent such as tetrahydrofuran and dioxane. ; Ester solvent such as ethyl acetate and butyl acetate; nitrile solvent such as acetonitrile; amide solvent such as dimethylformamide and N-methylpyrrolidone.
  • the reaction temperature can be, for example, 50 to 90 ° C., and the reaction time can be, for example, 2 to 24 hours.
  • the reaction pressure may be normal pressure, pressurization, or depressurization.
  • the reaction atmosphere may be an inert gas atmosphere such as nitrogen or argon, or may be a dry air atmosphere, a closed condition, or other conditions where water is not mixed.
  • the hydroxyl group equivalent of the polymer (A) is preferably 400 g / eq. As mentioned above, more preferably 450 g / eq. The above is preferable, and 4000 g / eq. Hereinafter, more preferably 3000 g / eq. It is as follows.
  • the curing agent (ii) preferably contains the polyisocyanate compound (d).
  • the polyisocyanate compound (d) has two or more isocyanate groups.
  • the polyisocyanate compound (d) one kind or two or more kinds can be used.
  • the diisocyanate compound having two isocyanate groups an alicyclic structure such as cyclohexanediisocyanate, dicyclohexylmethanediisocyanate, isophoronediisocyanate or the like can be used.
  • the polyisocyanate compound (d) preferably contains a polyisocyanate compound having three or more isocyanate groups.
  • the content of the polyisocyanate compound having 3 or more isocyanate groups is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more in the polyisocyanate compound (d).
  • the upper limit is 100% by mass.
  • the content of the curing agent (ii) is less than 50% by mass, preferably 40% by mass or less, more preferably 30% by mass or less, and further, in the total of the main agent (i) and the curing agent (ii). It is preferably 20% by mass or less, and the lower limit is, for example, 0.1% by mass.
  • the molar ratio (NCO / OH) of the hydroxyl group of the polymer (A) contained in the main agent (i) to the isocyanate group of the polyisocyanate compound (d) contained in the curing agent (ii) is preferably 0.8. As mentioned above, it is more preferably 0.9 or more, preferably 1.5 or less, and more preferably 1.2 or less.
  • the content of the urethane resin is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and the upper limit is 100% by mass in the resin contained in the resin molded product. ..
  • the content of the resin is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and the upper limit is 100% by mass in the resin molded product.
  • the dynamic friction force can be achieved, for example, by using a slippery imparting agent.
  • the slipper-imparting agent is preferably incompatible with the resin. Therefore, the difference between the solubility parameters of the slippery agent and the resin is preferably 2 (cal / cm 3 ) 0.5 or more, more preferably 2.5 (cal / cm 3 ) 0.5 or more, and further preferably 3 (cal / cm 3 ). / Cm 3 ) 0.5 or more, and the upper limit may be, for example, 10 (cal / cm 3 ) 0.5 or less and 8 (cal / cm 3 ) 0.5 or less.
  • the solubility parameter can be calculated using the Fedors formula based on the chemical structural formulas of the resin and the slipper-imparting agent (Polymer Engineering and Science, 1974, coll. 14, No. 12).
  • the slipper-imparting agent contains the compound (B) represented by the following formula (1).
  • R 1 and R 2 each independently represent a methyl group or a hydroxyl group.
  • n represents an integer from 1 to 3,000.
  • the slippery imparting agent (iii) may be contained in the urethane resin composition, and the mixing order of the main agent (i) and the curing agent (ii) is not particularly limited.
  • R 1 and R 2 are preferably methyl groups from the viewpoint of scratch resistance.
  • n is preferably 1 to 3,000, more preferably 5 to 2,500, and even more preferably 6 to 2,200.
  • the molecular weight of the compound (B) is, for example, 500 or more, more preferably 1,000 or more, still more preferably 5,000 or more, preferably 150,000 or less, more preferably 120,000 or less, still more preferably. It is 110,000 or less.
  • the molecular weight of the compound (B) is based on the kinematic viscosity of the compound (B) at 25 ° C. J. It can be obtained by Barry's formula.
  • the compound (B) may be mixed with the main agent (i) and the curing agent (ii) as it is, or may be mixed after being dispersed in a dispersion medium such as water in advance.
  • the content of the compound (B) is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, based on 100 parts by mass of the total of the main agent (i) and the curing agent (ii). It is more preferably 0.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.
  • the resin molded product can be formed by using a resin composition containing the resin (or the resin precursor) and the slipper-imparting agent.
  • the resin composition preferably contains the main agent (i) and the curing agent (ii) as the resin precursor.
  • the resin composition may contain the organic solvent (C).
  • the organic solvent (C) one kind or two or more kinds can be used, for example, aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and acetylacetone; tetrahydrofuran, dioxane and the like.
  • Ether solvent ester solvent such as ethyl acetate and butyl acetate
  • nitrile solvent such as acetonitrile
  • amide solvent such as dimethylformamide and N-methylpyrrolidone.
  • the content of the organic solvent (C) in the resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and preferably 80% by mass or less. It is preferably 70% by mass or less, more preferably 65% by mass or less.
  • the resin composition may contain another additive (D).
  • the other additive (D) include tackifiers, leveling agents, catalysts, plasticizers, stabilizers, fillers, pigments, dyes, flame retardants and the like.
  • the content thereof is, for example, 30% by mass or less, 10% by mass or less, 5% by mass or less, and the lower limit is 0% by mass, based on the total amount of the resin composition. ..
  • a laminate having a base material and the resin molded product is also included in the technical scope of the present invention.
  • the base material is not particularly limited, and wood; polyester resin, epoxy resin, polyamide resin, acrylic resin, polyolefin resin, polycarbonate resin, polyurethane resin, ABS resin, polyvinyl chloride resin, polystyrene resin, phenol resin, melamine resin. , Urea resin, alkyd resin and other synthetic or natural resins; metals such as aluminum, iron, copper, zinc, iron alloys, aluminum alloys, copper alloys and zinc alloys; glass; base materials such as ceramics can be used.
  • the shape of the molded product is not particularly limited, and the resin composition may have a film shape, a plate shape, or various three-dimensional shapes.
  • the molding method of the molded product is not particularly limited, and molding methods such as injection molding, extrusion molding, hollow molding, thermoforming, and inflation molding can be adopted.
  • the molded product may be a product (cured coating film) formed by applying the resin composition to an article and curing it. Examples of the method of applying the resin composition to an article include a dip coating method, a spin coating method, a flow coating method, a spray coating method, a roll coating method, a gravure roll coating method, an air doctor coating method, a blade coating method, and a wire doctor.
  • a coating method, a knife coating method, a reverse coating method, a transfer roll coating method, a microgravure coating method, a kiss coating method, a cast coating method, a slot orifice coating method, a calendar coating method, a die coating method and the like can be appropriately adopted.
  • the resin molded body and the laminated body are suitable for articles such as automobiles, automobile parts, home appliances, mobile phones, industrial supplies, medical supplies, optical members, robot supplies, packaging materials, OA equipment, and sports goods. Can be used.
  • the mixture is stirred for 3 hours while maintaining the temperature, and the main agent (i) containing a prepolymer (A-1) having a hydroxyl group at the molecular end having a hydroxyl group equivalent weight of 1954. -1) was obtained.
  • PTMG2000 represents polyoxytetramethylene glycol (PTMG2000, molecular weight 2,000, manufactured by Mitsubishi Chemical Corporation)
  • G3452 represents a polycarbonate polyol (G3452, number average molecular weight 2,000, manufactured by Asahi Kasei Co., Ltd.).
  • UH-200 represents a polycarbonate polyol (UH-200, average molecular weight 2,000, manufactured by Ube Industries, Ltd.)
  • T5652 represents a polycarbonate polyol (T5652, number average molecular weight 2,000, manufactured by Asahi Kasei Co., Ltd.).
  • T5651 represents a polycarbonate polyol (T5651, number average molecular weight 1,000, manufactured by Asahi Kasei Co., Ltd.), and UM-90 represents a polycarbonate polyol (UM-90, number average molecular weight 900, manufactured by Ube Industries, Ltd.), DN-902S. Represents an isocyanurate form of hexamethylene diisocyanate (Bernock DN-902S, manufactured by DIC Co., Ltd.).
  • Example 1 100 parts by mass of the main agent (i) and 5.3 parts by mass of the curing agent (ii) (isocyanurate form of hexamethylene diisocyanate (Bernock DN-902S)) were mixed so that the NCO / OH ratio was 1.10, and the mixture was further slipped.
  • a thermosetting urethane resin composition by mixing 0.5 parts by mass of a sex-imparting agent (iii) Wacker AK-1000 (dimethylpolysiloxane oil) and 1.5 parts by mass of a leveling agent (Silclean 3700, manufactured by Big Chemie Japan). I got the thing (1).
  • thermosetting urethane resin composition (1) is the same as in Example 1 except that the main agent (i), the curing agent (ii), and the slippering agent (iii) are changed as shown in Table 2 or Table 3. )-(8), comparative compositions (1)-(7) were obtained.
  • the obtained urethane resin composition and comparative composition were evaluated by the following methods.
  • thermosetting urethane resin compositions obtained in Examples and Comparative Examples were applied onto a PET film with a knife coater so that the solid content film thickness was 30 microns, and at 70 ° C. for 2 minutes, and further at 110 ° C. for 2 minutes. It was dried to prepare a polyurethane resin film.
  • a test piece of a polyurethane resin film having a width of 5 mm and a length of 50 mm was cut out into strips, and a tensile test was conducted using a tensile tester in an environment with a chuck distance of 40 mm, a tensile speed of 10 mm / sec, and a temperature of 23 ° C.
  • the stress at 100% elongation is 100% modulus, and the elongation at break is elongation.
  • the loss ratio of the amount of heat obtained from the difference between the amount of heat given when the test piece was pulled and the amount of heat released when the test piece was pulled back from the integrated value of the graph of the applied load and the amount of deformation was defined as the hysteresis loss.
  • HDI hexamethylene diisocyanate
  • hydrogenated MDI hydrogenated diphenylmethane diisocyanate
  • AK1000 dimethyl silicone oil (AK1000, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.)
  • AK10000 dimethyl silicone oil (AK100, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.)
  • AK100,000 dimethyl silicone oil (AK100,000, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.)
  • C800 represents a silicone emulsion (C800, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.).
  • KF53 represents methylphenyl silicone oil (KF-53, manufactured by Shinetsu Silicone Co., Ltd.)
  • BYK-333 represents polyether-modified polydimethylsiloxane (BYK-333, manufactured by Big Chemie Japan Co., Ltd.).
  • Examples 1 to 9 are examples of the present invention, and both flexibility and scratch resistance could be achieved at the same time.
  • Comparative Examples 1 to 3 are examples that do not satisfy the requirement for slipperiness
  • Comparative Examples 4 and 5 are examples that do not satisfy the requirement for hysteresis loss
  • Comparative Example 6 meets the requirements for 100% modulus and hysteresis loss. This was an unsatisfied example, and all had insufficient scratch resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Automation & Control Theory (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
  • Investigating Strength Of Materials By Application Of Mechanical Stress (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention aborde le problème de la flexibilité et de la résistance aux rayures. Un corps moulé en résine selon la présente invention présente un module de 100 % de 5 MPa ou moins, une perte d'hystérésis pendant 100 % de récupération d'étirement de 20 % ou moins, et une force de frottement dynamique de 2 kN ou moins.
PCT/JP2020/017111 2019-04-19 2020-04-20 Corps moulé en résine WO2020213746A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006160875A (ja) * 2004-12-07 2006-06-22 Yokohama Rubber Co Ltd:The ウレタン樹脂組成物
JP2006199795A (ja) * 2005-01-19 2006-08-03 Bando Chem Ind Ltd ウレタン製透明保護材、ウレタン製透明保護材の製造方法及び樹脂組成物
JP2007119749A (ja) * 2005-09-27 2007-05-17 Dai Ichi Kogyo Seiyaku Co Ltd 繊維積層体表皮層用ポリウレタン樹脂水分散体組成物、繊維積層体の製造方法及び合成皮革
WO2016204065A1 (fr) * 2015-06-18 2016-12-22 Dic株式会社 Composition durcissable bicomposant, agent adhésif de type bicomposant, agent de revêtement de type bicomposant, et stratifié
JP2019006936A (ja) * 2017-06-28 2019-01-17 三洋化成工業株式会社 ポリウレタン樹脂水性分散体
JP2019019314A (ja) * 2017-07-05 2019-02-07 宇部興産株式会社 エマルジョン組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005068528A1 (fr) * 2004-01-08 2005-07-28 Dutch Polymer Institute Polyurethannes, urees polyurethannes et polyurees leur utilisation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006160875A (ja) * 2004-12-07 2006-06-22 Yokohama Rubber Co Ltd:The ウレタン樹脂組成物
JP2006199795A (ja) * 2005-01-19 2006-08-03 Bando Chem Ind Ltd ウレタン製透明保護材、ウレタン製透明保護材の製造方法及び樹脂組成物
JP2007119749A (ja) * 2005-09-27 2007-05-17 Dai Ichi Kogyo Seiyaku Co Ltd 繊維積層体表皮層用ポリウレタン樹脂水分散体組成物、繊維積層体の製造方法及び合成皮革
WO2016204065A1 (fr) * 2015-06-18 2016-12-22 Dic株式会社 Composition durcissable bicomposant, agent adhésif de type bicomposant, agent de revêtement de type bicomposant, et stratifié
JP2019006936A (ja) * 2017-06-28 2019-01-17 三洋化成工業株式会社 ポリウレタン樹脂水性分散体
JP2019019314A (ja) * 2017-07-05 2019-02-07 宇部興産株式会社 エマルジョン組成物

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