WO2013061790A1 - 湿気硬化型ポリウレタンホットメルト樹脂組成物、接着剤及び物品 - Google Patents
湿気硬化型ポリウレタンホットメルト樹脂組成物、接着剤及び物品 Download PDFInfo
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- WO2013061790A1 WO2013061790A1 PCT/JP2012/076312 JP2012076312W WO2013061790A1 WO 2013061790 A1 WO2013061790 A1 WO 2013061790A1 JP 2012076312 W JP2012076312 W JP 2012076312W WO 2013061790 A1 WO2013061790 A1 WO 2013061790A1
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- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4255—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing oxyalkylated carbocyclic groups and polycarboxylic acids
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
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- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
Definitions
- the present invention relates to a moisture-curable polyurethane hot melt resin composition excellent in waterproofness, drop impact resistance, flexibility and the like, and an adhesive and an article using the same.
- moisture-curable polyurethane hot melt adhesives are solvent-free, various researches have been made to date, focusing on fiber bonding and building material lamination as environmentally friendly adhesives, and they are also widely used in industry.
- Examples of the adhesive include (a) 100 parts by weight of a polyurethane resin having a flow start temperature of 55 ° C. to 110 ° C. and (b) a saturated polyester resin having a Tg of 0 ° C. to 110 ° C. and a molecular weight of 10,000 to 25,000. 5 to 150 parts by weight, (c) 10 to 150 parts by weight of an epoxy resin having a softening point of 60 to 140 ° C. and a molecular weight of 700 to 3000, and (d) 10 to 200 parts by weight of an inorganic filler surface-treated with a coupling agent
- An adhesive using a heat-and-moisture resistant hot-melt adhesive composition characterized in that is formulated is disclosed (for example, see Patent Document 1).
- the adhesive has a heat-and-moisture resistance of a practically usable level.
- the water may penetrate into the article in a relatively short time, indicating that the waterproof performance is insufficient. was there.
- the moist heat resistant hot melt adhesive composition has the merit that it can be bonded even at low temperatures, but since the epoxy resin is used, the adhesive itself has insufficient flexibility or the article has dropped. In some cases, the adhesive layer may be peeled off.
- the problem to be solved by the present invention is to provide a moisture curable polyurethane hot melt resin composition having excellent waterproofness, drop impact resistance, flexibility and the like.
- the inventors of the present invention while pursuing research to solve the above-mentioned problems, paid attention to the polyol used for the urethane prepolymer, proceeded with earnest research, and completed the present invention.
- the present invention is a moisture curable polyurethane hot melt resin composition containing a urethane prepolymer having an isocyanate group obtained by reacting a polyol (A) and a polyisocyanate (B), the polyol (A) Is characterized in that it contains polyether polyol (A-1), crystalline polyester polyol (A-2), amorphous polyester polyol (A-3) and acrylic polyol (A-4).
- a moisture-curable polyurethane hot melt resin composition, and an adhesive and an article obtained using the same are provided.
- the adhesive obtained using the moisture-curable polyurethane hot melt resin composition of the present invention is waterproof, drop impact resistant, flexible, adhesive to various substrates, application workability, and shape retention after application. It has excellent performance and open time. Therefore, the adhesive obtained by using the moisture-curable polyurethane hot melt resin composition of the present invention can be suitably used not only for fiber bonding and building material lamination, but also for bonding optical members.
- the moisture curable polyurethane hot melt resin composition of the present invention comprises a polyether polyol (A-1), a crystalline polyester polyol (A-2), an amorphous polyester polyol (A-3), and an acrylic polyol (A-4). ) -Containing polyol (A) and polyisocyanate (B), and a urethane prepolymer having an isocyanate group obtained by reaction.
- the polyether polyol (A-1) is used to provide excellent workability, adhesion, waterproofness, flexibility, etc. by adjusting an appropriate melt viscosity and open time (bonding time) after coating. It is an essential component, and for example, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, ethylene oxide-modified polypropylene glycol and the like can be used.
- the number average molecular weight of the polyether polyol (A-1) is preferably in the range of 500 to 5,000 from the viewpoints of adhesiveness (initial adhesive strength, sampling adhesive strength) and appropriate open time after coating, and 700 A range of ⁇ 5,000 is more preferred.
- the number average molecular weight of the said polyether polyol was measured on condition of the following by the gel permeation chromatography (GPC) method.
- Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. “TSKgel G5000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 “TSKgel G4000” (7.8 mmID ⁇ 30 cm) ⁇ 1 “TSKgel G3000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
- the crystalline polyester polyol (A-2) is an essential component for imparting waterproofness, adhesiveness (initial adhesive strength), open time, and the like.
- the reaction between a compound having a hydroxyl group and a polybasic acid Can be used.
- “crystallinity” means an endothermic amount at an endothermic peak corresponding to a melting point under a temperature rising condition of 20 ° C./min in DSC (differential scanning calorimeter) measurement in accordance with JIS K 7121. It refers to those showing 20 J / g or more, and “amorphous” refers to other than that.
- hydroxyl group-containing compound examples include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, trimethylolpropane, trimethylolethane, and glycerin. Can do. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use butanediol, hexanediol, octanediol, and decanediol from the viewpoint of improving crystallinity and improving waterproofness and adhesiveness.
- the polybasic acid is preferably a dibasic acid.
- oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, 1,12-dodecanedicarboxylic acid and the like can be used.
- the number average molecular weight of the crystalline polyester polyol (A-2) is preferably in the range of 500 to 5,000, more preferably in the range of 1,000 to 4,000, from the viewpoint of waterproofness and adhesiveness.
- the number average molecular weight of the crystalline polyester polyol (A-2) is a value obtained by measurement in the same manner as the number average molecular weight of the polyether polyol (A-1).
- the glass transition temperature (Tg) of the crystalline polyester polyol (A-2) is preferably in the range of 40 to 130 ° C.
- the glass transition temperature of the crystalline polyester polyol (A-2) is a value measured by DSC in accordance with JIS K 7121-1987. Specifically, the glass transition temperature is within the differential scanning calorimeter ( A-2) was added, the temperature was raised to (Tg + 50 ° C.) at a rate of temperature increase of 10 ° C./minute, held for 3 minutes, and then rapidly cooled, and the midpoint glass transition temperature (Tmg) read from the obtained differential heat curve. ).
- the amount of the crystalline polyester polyol (A-2) used is 20 to 400 parts by mass with respect to 100 parts by mass of the ether polyol (A-1) from the viewpoints of flexibility, adhesiveness, open time, and the like.
- the range is preferable, the range of 25 to 300 parts by mass is more preferable, and the range of 30 to 230 parts by mass is particularly preferable.
- polycaprolactone polyol can also be used.
- polycaprolactone polyol for example, a product obtained by reacting the compound having a hydroxyl group with ⁇ -caprolactone can be used.
- the number average molecular weight is preferably in the range of 20,000 to 200,000.
- the amorphous polyester polyol (A-3) is provided with excellent workability, adhesiveness, waterproofness, flexibility, etc. by adjusting an appropriate melt viscosity and open time (bonding time) after coating.
- a reaction product of the following compound having a hydroxyl group and a polybasic acid can be used.
- Examples of the compound having a hydroxyl group include ethylene glycol, propylene glycol, 1,4-butanediol, pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, Hexanediol, neopentyl glycol, hexamethylene glycol, glycerin, trimethylolpropane, bisphenol A and bisphenol F, and alkylene oxide adducts thereof can be used.
- the added mole number of the alkylene oxide is preferably 2 to 10 moles, more preferably 4 to 8 moles.
- adipic acid As the polybasic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, sebacic acid, undecanedicarboxylic acid, hexahydroterephthalic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc. should be used. Can do.
- the number average molecular weight of the amorphous polyester polyol (A-3) is preferably in the range of 500 to 5,000, preferably 1,000 to 4,000, from the viewpoint of improving waterproofness, adhesiveness, flexibility and the like. Is more preferable, and the range of 1,000 to 3,000 is still more preferable.
- the glass transition temperature of the amorphous polyester polyol (A-3) is preferably in the range of ⁇ 70 to ⁇ 10 ° C. from the viewpoint of improving waterproofness, adhesiveness, flexibility and the like.
- the glass transition temperature of the amorphous polyester polyol (A-3) is the same as the method for measuring the glass transition temperature (Tg) of the crystalline polyester polyol (A-2).
- the amount of the amorphous polyester polyol (A-3) used is 10 to 300 with respect to 100 parts by mass of the ether polyol (A-1) from the viewpoint of improving waterproofness, adhesiveness, flexibility and the like.
- the range of parts by mass is preferable, the range of 20 to 250 parts by mass is more preferable, and the range of 25 to 180 parts by mass is still more preferable.
- the acrylic polyol (A-4) is an essential component for imparting excellent workability, waterproofness, adhesiveness, etc. by adjusting an appropriate open time (bonding time) after coating. It is obtained by polymerizing a (meth) acrylic compound which essentially contains a (meth) acrylic compound.
- (meth) acrylic compound refers to one or both of a methacrylic compound and an acrylic compound.
- (meth) acrylic compound having a hydroxyl group for example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like can be used.
- Examples of other (meth) acrylic compounds include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth).
- Acrylate neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, etc.
- (meth) acrylic compounds may be used alone or in combination of two or more.
- a (meth) acrylic compound having a hydroxyl group and an alkyl (meth) acrylate it is preferable to use a (meth) acrylic compound having a hydroxyl group and an alkyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate, Methyl (meth) acrylate and n-butyl (meth) acrylate are preferably used.
- the number average molecular weight of the acrylic polyol (A-4) is preferably from 5,000 to 50,000, particularly preferably from 10,000 to 30,000, from the viewpoint of improving waterproofness, adhesiveness, open time, and the like.
- the number average molecular weight of the acrylic polyol (A-4) is the same as the method for measuring the number average molecular weight of the polyether polyol (A-1).
- the glass transition temperature of the acrylic polyol (A-4) is preferably in the range of 30 to 120 ° C. from the viewpoint of improving waterproofness, adhesiveness (particularly, initial adhesive strength due to improved cohesive strength), open time, etc. A range of 50 to 80 ° C. is more preferable.
- the glass transition temperature of the acrylic polyol (A-4) is the same as the method for measuring the glass transition temperature (Tg) of the crystalline polyester polyol (A-2).
- the amount of the acrylic polyol (A-4) used is in the range of 20 to 400 parts by mass with respect to 100 parts by mass of the ether polyol (A-1) from the viewpoint of improving waterproofness, adhesiveness and open time.
- the range of 40 to 280 parts by mass is more preferable, and the range of 45 to 150 parts by mass is particularly preferable.
- the polyol (A) contains the above (A-1) to (A-4), but polycarbonate polyol, polybutadiene polyol, dimer diol, etc. are used in combination as long as the effects of the present invention are not impaired. May be.
- a diisocyanate for example, an aromatic polyisocyanate such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, Aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used.
- diphenylmethane diisocyanate is preferable from the viewpoint of reactivity and adhesiveness.
- the amount of the polyisocyanate (B) used is preferably in the range of 10 to 50 parts by mass with respect to 100 parts by mass of the moisture-curable polyurethane hot melt resin composition of the present invention from the viewpoint of viscosity and the like. A range of ⁇ 30 parts by mass is more preferred.
- the urethane prepolymer (i) is obtained by reacting the polyol (A) and the polyisocyanate (B). In the casing or adherend to which the urethane prepolymer is applied in the air. It has an isocyanate group capable of reacting with existing moisture to form a crosslinked structure at the polymer terminal or in the molecule.
- the said urethane prepolymer (i) heats, after dripping the mixture of the said polyol (A) to the reaction container containing the said polyisocyanate (B), and has the said polyisocyanate (B), for example. It can manufacture by making it react on the conditions from which an isocyanate group becomes excess with respect to the hydroxyl group which the said polyol (A) has.
- the equivalent ratio of the isocyanate group of the polyisocyanate (B) and the hydroxyl group of the polyol (A) is waterproof or adhesive. From the viewpoints of properties and flexibility, a range of 1.1 to 5.0 is preferable, and a range of 1.5 to 3.0 is more preferable.
- the urethane prepolymer (i) can be usually produced in the absence of a solvent, but may be produced by reacting the polyol (A) and the polyisocyanate (B) in an organic solvent.
- an organic solvent such as ethyl acetate, n-butyl acetate, methyl ethyl ketone, and toluene that does not inhibit the reaction can be used. It is necessary to remove the organic solvent.
- a urethanization catalyst can be used as necessary.
- the urethanization catalyst can be appropriately added at any stage of the reaction.
- urethanization catalyst examples include nitrogen-containing compounds such as triethylamine, triethylenediamine and N-methylmorpholine; metal salts such as potassium acetate, zinc stearate and tin octylate; organometallic compounds such as dibutyltin dilaurate and the like. Can do.
- the isocyanate group content (hereinafter abbreviated as “NCO%”) of the urethane prepolymer (i) obtained by the above method is as follows: 1. From the viewpoint of further improving waterproofness, adhesiveness, and flexibility. The range of 5 to 8.0% is preferable, the range of 1.7 to 5.0 is more preferable, and the range of 1.8 to 3.0 is particularly preferable.
- the NCO% of the urethane prepolymer (i) is a value measured by potentiometric titration in accordance with JIS K1603-1.
- the melt viscosity at 125 ° C. is preferably in the range of 1,000 to 50,000 mPa ⁇ s, and preferably in the range of 2,000 to 10,000 mPa ⁇ s. More preferred.
- the melt viscosity at 125 ° C. is a value measured with a cone plate viscometer (manufactured by ICI).
- the softening point of the urethane prepolymer (i) is preferably in the range of 30 to 120 ° C. from the viewpoint of waterproofness, adhesiveness and workability.
- the softening point refers to the temperature at which the fluid starts to flow and loses cohesion when the temperature of the ureta prepolymer is raised stepwise. Further, the softening point of the urethane prepolymer (i) indicates a value obtained by a ring and ball method based on JIS K 5902.
- the moisture curable polyurethane hot melt resin composition of the present invention may be composed of only the urethane prepolymer, but may contain other additives as necessary.
- antioxidants examples include antioxidants, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent brighteners, silane coupling agents, waxes, thermoplastic resins, and the like. be able to.
- the adhesive obtained by using the moisture-curable polyurethane hot melt resin composition of the present invention is waterproof, drop impact resistance, flexibility, adhesion to various substrates, application workability, after application It has excellent shape retention and open time, and can be suitably used not only for fiber bonding and building material lamination, but also for bonding optical members.
- Examples of the mode used for laminating the optical member include sealing agents for mobile phones, personal computers, game machines, televisions, car navigation systems, camera speakers, and the like.
- the moisture-curable polyurethane hot melt resin composition is heated and melted in a temperature range of 50 to 130 ° C., and the composition is applied onto one member, and then the composition A method of obtaining an article by attaching another member on an object is mentioned.
- the member examples include glass, acrylic resin, urethane resin, silicon resin, epoxy resin, fluorine resin, polystyrene resin, polyester resin, polysulfone resin, polyarylate resin, and polyvinyl chloride resin. , Cycloolefin resins such as polyvinylidene chloride and norbornene, polyolefin resins, polyimide resins, alicyclic polyimide resins, cellulose resins, polycarbonate (PC), polybutylene terephthalate (PBT), modified polyphenylene ether (modified) PPE), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), lactic acid polymer, acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene copolymer resin (AS), etc. It can be used shall. Further, the member may be subjected to corona treatment, plasma treatment, primer treatment, or the like, if necessary.
- the moisture curable polyurethane hot melt resin composition for example, a roll coater, a spray coater, a T-tie coater, a knife coater, a comma coater, or the like can be used.
- the moisture-curable polyurethane hot melt resin composition of the present invention has low viscosity and shape retention after application, it can also be applied by a method such as dispenser, ink jet printing, screen printing, and offset printing. Can do.
- These application methods are preferable because the moisture-curable polyurethane hot melt resin composition can be applied to the part on the member where it is desired to be applied, so that no loss such as punching occurs.
- the moisture curable polyurethane hot melt resin composition is continuously formed on the member in various shapes such as dotted, linear, triangular, square, round, and curved. Or can be formed intermittently or intermittently.
- the thickness of the adhesive layer using the moisture curable polyurethane hot melt resin composition can be set according to the intended use, but can be preferably set in the range of 10 ⁇ m to 5 mm, for example.
- the aging conditions after the bonding can be appropriately determined, for example, at a temperature of 20 to 80 ° C., a relative humidity of 50 to 90% RH, and 0.5 to 5 days.
- Example 1 In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 15 parts by mass of polypropylene glycol (number average molecular weight; 1,000, hereinafter abbreviated as “PPG1000”), polypropylene glycol (several Average molecular weight: 2,000, hereinafter abbreviated as “PPG2000”) 15 parts by mass, crystalline PEs-1 (reaction of 1,6-hexanediol and 1,12-dodecanedicarboxylic acid, number average molecular weight; 3,500) 10 parts by mass, amorphous PEs-1 (6 mol adduct of propylene oxide of bisphenol A, sebacic acid, isophthalic acid, number average molecular weight; 2,000) 15 parts by mass, acrylic 30 parts by weight of polyol-1 was charged, and the water content in the polyol mixture was 0.05% by mass or less at 100 °
- Examples 2 to 8 Comparative Examples 1 to 4
- a urethane prepolymer was obtained in the same manner as in Example 1 except that the kind and / or amount of polyol and the amount of polyisocyanate were changed as shown in Tables 1 to 3.
- acrylic is applied under a condition that the impact is applied five times at a load of 300 g / height of 30 cm from the adherend side with a DuPont-type drop impact tester from the adherend side.
- the drop impact resistance was evaluated by the presence or absence of peeling of the plate. The case where peeling did not occur was evaluated as “ ⁇ ”, and the case where peeling occurred was evaluated as “x”.
- the moisture curable polyurethane hot melt resin compositions of Examples 1 to 8 of the present invention have waterproofness, drop impact resistance, flexibility, adhesion to various substrates, application workability, and retention after application. It was found that it was excellent in type and open time.
- Comparative Example 1 was an embodiment that did not contain the polyether polyol (A-1), but was found to be poor in waterproofness, drop impact resistance, flexibility and the like.
- Comparative Example 2 was an embodiment that did not contain the crystalline polyester polyol (A-2), but was found to have poor waterproofness, drop impact resistance, and the like.
- Comparative Example 3 was an embodiment that did not contain the amorphous polyester polyol (A-3), but was found to have poor waterproofness, drop impact resistance, flexibility, and the like.
- Comparative Example 4 is an embodiment that does not contain the acrylic polyol (A-4), but it was found that the waterproof property was particularly poor.
Abstract
Description
また、前記耐湿熱性ホットメルト接着剤組成物は、低温時においても接着できるというメリットを有するものの、エポキシ樹脂を用いているため、接着剤自体の柔軟性が不十分であったり、物品が落下した場合には接着剤層が剥離してしまう等の問題点もあった。
従って、本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物を用いて得られた接着剤は、繊維ボンディング・建材ラミネーション用途のみならず、光学用部材の貼り合せに好適に用いることができる。
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度0.4質量%のテトラヒドロフラン溶液)
標準試料:下記の標準ポリスチレンを用いて検量線を作成した。
東ソー株式会社製「TSKgel 標準ポリスチレン A-500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A-2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F-1」
東ソー株式会社製「TSKgel 標準ポリスチレン F-2」
東ソー株式会社製「TSKgel 標準ポリスチレン F-4」
東ソー株式会社製「TSKgel 標準ポリスチレン F-10」
東ソー株式会社製「TSKgel 標準ポリスチレン F-20」
東ソー株式会社製「TSKgel 標準ポリスチレン F-40」
東ソー株式会社製「TSKgel 標準ポリスチレン F-80」
東ソー株式会社製「TSKgel 標準ポリスチレン F-128」
東ソー株式会社製「TSKgel 標準ポリスチレン F-288」
東ソー株式会社製「TSKgel 標準ポリスチレン F-550」
<アクリルポリオール-1の合成>
温度計、攪拌機及び冷却管を備えた反応容器に、メチルエチルケトン300質量部を入れ、容器内温度を80℃にした後、メチルメタクリレート340質量部、n-ブチルメタクリレート150質量部、2-ヒドロキシエチルメタクリレート10質量部、アゾビスイソブチロニトリル8.5質量部をメチルエチルケトン160質量部に溶解したものを添加、混合し、16時間反応させることによって、アクリルポリオール-1(不揮発分:52質量%、粘度;2,000mPa・s(23℃)、数平均分子量;20,000)を得た。
温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに、ポリプロピレングリコール(数平均分子量;1,000、以下「PPG1000」と略す。)15質量部、ポリプロピレングリコール(数平均分子量;2,000、以下「PPG2000」と略す。)15質量部、結晶性PEs-1(1,6-ヘキサンジオールと1,12-ドデカンジカルボン酸とを反応させたもの、数平均分子量;3,500)10質量部、非晶性PEs-1(ビスフェノールAのプロピレンオキサイド6モル付加物と、セバシン酸、イソフタル酸を反応させたもの、数平均分子量;2,000)15質量部、アクリルポリオール-1を30質量部仕込み、減圧下100℃でポリオール混合物中の水分含有率が0.05質量%以下となるまで脱水した。
次いで、容器内温度70℃に冷却後、4,4’-ジフェニルメタンジイソシアネート(MDI)15.5質量部を加え、100℃まで昇温して、NCO基含有率が一定となるまで約3時間反応させて、イソシアネート基を有するウレタンプレポリマーを得た。
ポリオールの種類及び/又は量、ポリイソシアネートの量を表1~3に示す通りに変更した以外は、実施例1と同様にしてウレタンプレポリマーを得た。
実施例及び比較例で得られたウレタンプレポリマーを120℃に溶融し、120℃に予め加熱された0.6mm内径のディスペンサーニードル(武蔵エンジニアリング株式会社製「VALVE MASTER ME-5000VT」)を用いて吐出圧力:0.3MPa、速度:50mm/秒にて10秒吐出した際の塗布量(g)により、塗布作業性を以下のように判断した。また、上記と同様の条件にて、筐体(アクリル板)に塗布した直後の接着剤層の高さ(mm)で、塗布後の保型性を以下のように判断した。また、該保型性の試験において、塗布後を基点とし、1分毎に指触にてタックの有無を確認し、表面のタック感がなくなるまでの時間(分)を測定し、オープンタイムについて以下のように判断した。
<塗布作業性>
「○」;1.0g以上
「△」;0.6g以上1.0g未満
「×」;0.6g未満
<塗布後の保型性>
「○」;0.5mm以上
「△」;0.3mm以上0.5mm未満
「×」;0.3mm未満
<オープンタイム>
「○」;4分以上10分未満
「×」;4分未満及び10分以上
上記[塗布後の保型性、オープンタイムの評価方法]で得られた接着剤層の機械的特性(100%モジュラス(MPa)、破断点応力(MPa)、破断点伸度(%))をJIS K-7311に準拠して測定し、100%モジュラスを基準に以下のように判断した。
「○」;5MPa以下
「△」;5MPaを超えて7MPa以下
「×」;7MPaを超える
実施例及び比較例で得られたウレタンプレポリマーを120℃に溶融させて、ロールコーターにて200μm厚みのコロナ処理PET上に100μmにて塗布し、各種基材(ABS(アクリロニトリル-ブタジエン-スチレン共重合樹脂)板、PC(ポリカーボネート)板、アクリル板)と貼り合せて、それぞれ23℃、65%RHの恒温槽に3日間放置し、その後180℃剥離強度(N/inch)をJIS K-7311に準拠して測定した。
実施例及び比較例で得られたウレタンプレポリマーを120℃に溶融し、120℃に予め加熱された0.6mmΦ内径のディスペンサーニードル(武蔵エンジニアリング製「VALVE MASTER ME-5000VT」)を用いて、アクリル板上に縦4cm、横4cm、厚み2mmの正方形を描く様にビード上に塗布して、ABS板(5cm×5cm)を貼り合せた後、温度23℃、相対湿度65%の恒温恒湿槽中に3日間放置した。
次いで、温度23℃、相対湿度50%の環境下で、デュポン式落下衝撃試験機にて被着体側から撃芯を介して、荷重300g/高さ30cmで衝撃を5回与える条件にて、アクリル板の剥がれの発生の有無で、耐落下衝撃性を評価した。なお、剥がれが発生しなかったものは「○」、剥がれが発生したものを「×」と評価した。
前記[耐落下衝撃性の評価方法]にて作成したサンプルを用いて、水浸漬(温度23℃、0,5時間)後の内部への水侵入の有無を、JIS IPX-7に準拠して行い、防水性を以下のように評価した。
「○」;水の侵入がない。
「×」;水の侵入がある。
「PTMG1000」;ポリテトラメチレングリコール、数平均分子量;1,000
「PTMG2000」;ポリテトラメチレングリコール、数平均分子量;2,000
「結晶性PEs-2」;1,6-ヘキサンジオールとアジピン酸とを反応させたもの、数平均分子量2,000
Claims (9)
- ポリオール(A)とポリイソシアネート(B)を反応させて得られるイソシアネート基を有するウレタンプレポリマーを含有する湿気硬化型ポリウレタンホットメルト樹脂組成物であって、前記ポリオール(A)が、ポリエーテルポリオール(A-1)、結晶性ポリエステルポリオール(A-2)、非晶性ポリエステルポリオール(A-3)及びアクリルポリオール(A-4)を含有するものであることを特徴とする湿気硬化型ポリウレタンホットメルト樹脂組成物。
- 前記アクリルポリオール(A-4)の数平均分子量が、5,000~50,000の範囲である請求項1記載の湿気硬化型ポリウレタンホットメルト樹脂組成物。
- 前記アクリルポリオール(A-4)のガラス転移温度が、30~120℃の範囲である請求項1記載の湿気硬化型ポリウレタンホットメルト樹脂組成物。
- 前記アクリルポリオール(A-4)が、水酸基を有する(メタ)アクリル化合物及び(メタ)アクリル酸アルキルエステルを重合して得られるものである請求項1記載の湿気硬化型ポリウレタンホットメルト樹脂組成物。
- 前記アクリルポリオール(A-4)の使用量が、前記ポリエーテルポリオール(A-1)100質量部に対して、20~400質量部の範囲である請求項1記載の湿気硬化型ポリウレタンホットメルト樹脂組成物。
- 前記非晶性ポリエステルポリオール(A-3)が、ビスフェノールAのアルキレンオキサイド付加物と、多塩基酸とを反応させて得られるものである請求項1記載の湿気硬化型ポリウレタンホットメルト樹脂組成物。
- 前記非晶性ポリエステルポリオール(A-3)の使用量が、前記ポリエーテルポリオール(A-1)100質量部に対して、10~300質量部の範囲である請求項1記載の湿気硬化型ポリウレタンホットメルト樹脂組成物。
- 請求項1~7のいずれか1項記載の湿気硬化型ポリウレタンホットメルト樹脂組成物を用いて得られたことを特徴とする接着剤。
- 少なくとも2つの部材を請求項8記載の接着剤で貼り合せたことを特徴とする物品。
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CN201280052113.5A CN103890032B (zh) | 2011-10-24 | 2012-10-11 | 湿气固化型聚氨酯热熔树脂组合物、胶粘剂及物品 |
KR1020147003743A KR101596475B1 (ko) | 2011-10-24 | 2012-10-11 | 습기 경화형 폴리우레탄 핫멜트 수지 조성물, 접착제 및 물품 |
US14/352,017 US9670391B2 (en) | 2011-10-24 | 2012-10-11 | Moisture-curable polyurethane hot-melt resin composition, adhesive, and article |
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JP2015003974A (ja) * | 2013-06-20 | 2015-01-08 | Dic株式会社 | 接着材及び接着性不織布 |
WO2015045635A1 (ja) * | 2013-09-27 | 2015-04-02 | Dic株式会社 | 製本用接着剤 |
JP2015196768A (ja) * | 2014-04-01 | 2015-11-09 | 積水フーラー株式会社 | 湿気硬化型ホットメルト接着剤 |
WO2015190276A1 (ja) * | 2014-06-13 | 2015-12-17 | 横浜ゴム株式会社 | 反応性ホットメルト接着剤組成物及びこれを用いる自動車灯具 |
JP2016000785A (ja) * | 2014-06-12 | 2016-01-07 | Dic株式会社 | 湿気硬化型ポリウレタンホットメルト接着剤 |
JP2016074826A (ja) * | 2014-10-07 | 2016-05-12 | Dic株式会社 | 積層体の製造方法及び化粧造作部材 |
JP2016121214A (ja) * | 2014-12-24 | 2016-07-07 | Dic株式会社 | 湿気硬化型ポリウレタンホットメルト接着剤及び製本用接着剤 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10500708A (ja) * | 1994-04-12 | 1998-01-20 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 反応性ワックス含有湿分硬化性ホットメルト組成物 |
JP2000344852A (ja) * | 1999-06-07 | 2000-12-12 | Sekisui Chem Co Ltd | 湿気硬化型ホットメルト組成物 |
JP2003515637A (ja) * | 1999-12-01 | 2003-05-07 | エイチ・ビー・フラー・ライセンシング・アンド・ファイナンシング・インコーポレイテッド | 改良された反応型ホットメルト接着剤 |
JP2005179422A (ja) * | 2003-12-17 | 2005-07-07 | Dainippon Ink & Chem Inc | 無溶剤型湿気硬化性ポリウレタン樹脂、それを用いた積層物、及び該積層物の製造方法 |
JP2005314445A (ja) * | 2004-04-27 | 2005-11-10 | Sanyo Chem Ind Ltd | 反応性ホットメルト接着剤 |
WO2009107301A1 (ja) * | 2008-02-27 | 2009-09-03 | Dic株式会社 | 透湿フィルム、その製造方法及びそれを用いた積層体 |
JP2010528160A (ja) * | 2007-05-24 | 2010-08-19 | エイチ.ビー.フラー カンパニー | 湿気硬化型ポリウレタンホットメルト接着剤組成物 |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6191212B1 (en) * | 1990-10-11 | 2001-02-20 | Henkel Kommanditgesellschaft Auf Aktien | Moisture-curing hotmelt adhesives |
JPH11286532A (ja) * | 1991-10-18 | 1999-10-19 | Morton Thiokol Inc | 熱可塑性エラストマーの製造方法 |
US5696179A (en) * | 1994-10-19 | 1997-12-09 | Dsm, N.V. | Silane oligomer and radiation curable coating composition containing the oligomer |
DE19963585A1 (de) * | 1999-12-29 | 2001-07-12 | Dupont Performance Coatings | Schmelzklebstoff-Zusammensetzung und Verfahren zum Verkleben von Substraten |
US6503981B2 (en) * | 2000-12-22 | 2003-01-07 | E. I. Du Pont De Nemours And Company | Polyurethane based thermoreactive hot-melt adhesives |
JP4865157B2 (ja) | 2001-07-19 | 2012-02-01 | 日東シンコー株式会社 | 耐湿熱性ホットメルト接着剤組成物 |
US20040214978A1 (en) * | 2003-04-22 | 2004-10-28 | Rosin Michael L. | Moisture-curing, hot-melt polyurethane adhesive |
CN100523111C (zh) * | 2004-04-09 | 2009-08-05 | 大日本油墨化学工业株式会社 | 湿气固化型聚氨酯热熔粘合剂 |
DE102005016516A1 (de) * | 2005-04-08 | 2006-10-12 | Klebchemie M.G. Becker Gmbh & Co. Kg | Mehrstufig härtende Oberflächenbeschichtung |
CN101180181B (zh) * | 2005-05-25 | 2012-06-06 | H.B.富勒公司 | 制备防水层叠体的方法 |
KR100591638B1 (ko) * | 2005-12-07 | 2006-06-21 | 주식회사 백산 | 미세기공이 형성된 무용제형 폴리우레탄 발포체 및 이를활용한 인조피혁 제조방법 |
WO2008026513A1 (fr) * | 2006-08-31 | 2008-03-06 | Ube Industries, Ltd. | Composition réactive thermofusible et article moulé l'utilisant |
JP5194518B2 (ja) | 2007-03-30 | 2013-05-08 | Dic株式会社 | 湿気硬化型ポリウレタンホットメルト接着剤及びそれを用いた造作材 |
JP4240158B1 (ja) | 2007-07-19 | 2009-03-18 | Dic株式会社 | 湿気硬化型ポリウレタンホットメルト接着剤及びそれを用いた積層体ならびに透湿フィルム |
ATE475697T1 (de) * | 2008-02-27 | 2010-08-15 | Sika Technology Ag | Kaschierklebstoff zur entformung bei erhöhter temperatur |
KR101601996B1 (ko) * | 2008-04-07 | 2016-03-17 | 도요보 가부시키가이샤 | 면상 발열체용 도전성 페이스트 및 이를 이용한 인쇄 회로, 면상 발열체 |
US8277601B2 (en) * | 2008-12-12 | 2012-10-02 | Henkel Corporation | Reactive hot melt adhesive |
JP5644592B2 (ja) * | 2011-03-07 | 2014-12-24 | 日立化成株式会社 | 接着剤 |
CN104245769B (zh) * | 2012-04-12 | 2016-08-17 | Dic株式会社 | 湿气固化型聚氨酯热熔树脂组合物、粘接剂和物品 |
-
2012
- 2012-10-03 TW TW101136441A patent/TWI534165B/zh active
- 2012-10-11 WO PCT/JP2012/076312 patent/WO2013061790A1/ja active Application Filing
- 2012-10-11 CN CN201280052113.5A patent/CN103890032B/zh active Active
- 2012-10-11 KR KR1020147003743A patent/KR101596475B1/ko active IP Right Grant
- 2012-10-11 US US14/352,017 patent/US9670391B2/en active Active
- 2012-10-11 JP JP2013506969A patent/JP5321931B1/ja active Active
- 2012-10-11 MY MYPI2014700922A patent/MY167733A/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10500708A (ja) * | 1994-04-12 | 1998-01-20 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 反応性ワックス含有湿分硬化性ホットメルト組成物 |
JP2000344852A (ja) * | 1999-06-07 | 2000-12-12 | Sekisui Chem Co Ltd | 湿気硬化型ホットメルト組成物 |
JP2003515637A (ja) * | 1999-12-01 | 2003-05-07 | エイチ・ビー・フラー・ライセンシング・アンド・ファイナンシング・インコーポレイテッド | 改良された反応型ホットメルト接着剤 |
JP2005179422A (ja) * | 2003-12-17 | 2005-07-07 | Dainippon Ink & Chem Inc | 無溶剤型湿気硬化性ポリウレタン樹脂、それを用いた積層物、及び該積層物の製造方法 |
JP2005314445A (ja) * | 2004-04-27 | 2005-11-10 | Sanyo Chem Ind Ltd | 反応性ホットメルト接着剤 |
JP2010528160A (ja) * | 2007-05-24 | 2010-08-19 | エイチ.ビー.フラー カンパニー | 湿気硬化型ポリウレタンホットメルト接着剤組成物 |
WO2009107301A1 (ja) * | 2008-02-27 | 2009-09-03 | Dic株式会社 | 透湿フィルム、その製造方法及びそれを用いた積層体 |
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WO2015045635A1 (ja) * | 2013-09-27 | 2015-04-02 | Dic株式会社 | 製本用接着剤 |
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US9487687B2 (en) | 2013-09-27 | 2016-11-08 | Dic Corporation | Bookbinding adhesive |
US20160251553A1 (en) * | 2013-10-04 | 2016-09-01 | Luna Innovations Incorporated | Fluid resistant, high performance reactive hot melt sealant and/or adhesive compositions |
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MY167733A (en) | 2018-09-24 |
JP5321931B1 (ja) | 2013-10-23 |
US9670391B2 (en) | 2017-06-06 |
CN103890032A (zh) | 2014-06-25 |
KR20140040269A (ko) | 2014-04-02 |
CN103890032B (zh) | 2016-05-04 |
TW201319107A (zh) | 2013-05-16 |
TWI534165B (zh) | 2016-05-21 |
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