WO2013153907A1 - 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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Definitions
- the present invention relates to a moisture curable polyurethane hot melt resin composition excellent in waterproofness, quick curing, 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.
- water may enter the laminated body in a relatively short time, and the waterproof performance is insufficient.
- the heat-and-moisture resistant hot melt adhesive composition has the merit that it can be bonded even at a low temperature, but cannot be used practically in a scene where rapid curing is desired, and since an epoxy resin is used, an adhesive.
- the flexibility of itself is insufficient and the use that can be used is limited.
- the problem to be solved by the present invention is to provide a moisture-curable polyurethane hot-melt resin composition that is excellent in waterproofness, fast-curing property, flexibility and the like.
- the inventors of the present invention while pursuing research to solve the above problems, paid attention to polyols and curing catalysts used for urethane prepolymers and proceeded earnestly to complete the present invention.
- the present invention relates to a polyol (A) containing a polyether polyol (A-1), a crystalline polyester polyol (A-2), an amorphous polyester polyol (A-3) and an acrylic polyol (A-4).
- Moisture-curable polyurethane hot comprising a urethane prepolymer (i) having an isocyanate group obtained by reacting polyisocyanate (B) with a curing catalyst (ii) represented by the following general formula (1)
- a melt resin composition, and an adhesive and an article obtained by using the melt resin composition are provided.
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group, and n independently represents an integer of 1 to 6)
- the adhesive obtained using the moisture curable polyurethane hot melt resin composition of the present invention is waterproof, fast curable, flexible, adhesive to various substrates, application workability, and shape retention after application. , Is excellent in 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 further contains an acrylic resin (iii), excellent drop impact resistance is imparted to an article obtained by using the acrylic resin (iii). be able to.
- 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 a urethane prepolymer (i) having an isocyanate group obtained by reacting a polyol (A) containing polyisocyanate (B) and a curing catalyst (ii) represented by the following general formula (1). is there.
- the polyether polyol (A-1) is provided with excellent workability, adhesiveness, waterproofness, flexibility and the like by adjusting an appropriate melt viscosity and open time (bonding time) after coating.
- 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 (particularly initial adhesive strength and final adhesive strength) and appropriate open time after coating.
- the range of 700 to 5,000 is more preferable.
- the number average molecular weight of the said polyether polyol shows the value measured on condition of the following by 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 (especially, initial adhesive strength), appropriate open time, and the like.
- a reaction product with an acid can be used.
- crystallization heat or heat of fusion can be confirmed in DSC (differential scanning calorimeter) measurement in accordance with JIS K 7121. Indicates that the peak cannot be confirmed.
- 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.
- polybasic acid for example, 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 crystal transition temperature is measured in the differential scanning calorimeter. Neutral polyester polyol (A-2) was added, the temperature was raised to (Tg + 50 ° C.) at a temperature rising rate of 10 ° C./min, held for 3 minutes, and then rapidly cooled, and the intermediate glass read from the obtained differential heat curve The transition temperature (Tmg) is indicated.
- the amount of the crystalline polyester polyol (A-2) used is 20 to 150 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, and the range of 30 to 100 parts by mass is more 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 number average molecular weight of the amorphous polyester polyol (A-3) 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 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 20 to 100 parts by mass with respect to 100 parts by mass of the ether polyol (A-1) from the viewpoint of improving waterproofness and flexibility, particularly adhesiveness.
- the range of 150 parts by mass is preferable, the range of 25 to 130 parts by mass is more preferable, and the range of 55 to 100 parts by mass is still more preferable.
- the acrylic polyol (A-4) has an excellent workability, waterproofness, adhesiveness, etc. by adjusting an appropriate open time (bonding time) after coating, and has a hydroxyl group (meth) It is obtained by polymerizing a (meth) acrylic compound containing an acrylic compound as an essential component.
- (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 acrylic polyol (A-4) is used in an amount 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 and open time, particularly adhesiveness.
- the range is preferable, the range of 25 to 200 parts by mass is more preferable, and the range of 35 to 150 parts by mass is particularly preferable.
- the polyol (A) contains the above (A-1) to (A-4), but other than polycarbonate polyol, polybutadiene polyol, dimer diol, etc., as long as the effects of the present invention are not impaired. These polyols may be used in combination.
- 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 referred to as NCO%) of the urethane prepolymer (i) obtained by the above method is 1.5 to 8.0% from the viewpoint of further improving waterproofness, adhesiveness and flexibility. 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 curing catalyst (ii) is for improving the fast curability without adversely affecting waterproofness, flexibility, adhesiveness, etc., and it is essential to use one represented by the following general formula (1). It is.
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group, and n independently represents an integer of 1 to 6)
- Examples of the curing catalyst (ii) include dimorpholinodiethyl ether represented by the following general formula (2) and bis (2, 2 represented by the following structural formula (3) from the viewpoint of improving rapid curability and thermal stability. It is particularly preferred to use 6-dimethylmorpholinoethyl) ether.
- the amount of the curing catalyst (ii) used is 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the urethane prepolymer (ii), from the viewpoint of improving fast curability and production stability.
- the range is preferable, and the range of 0.05 to 2.0 parts by mass is more preferable.
- the acrylic resin (iii) is an essential component particularly for imparting drop impact resistance, and is obtained by polymerizing a (meth) acrylic compound.
- the (meth) acryl compound can be the same as the (meth) acryl compound used in the acrylic polyol (A-4).
- the (meth) acrylic compound used as a raw material for the acrylic resin (iii) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms and / or a (meth) acrylate having a hydroxyl group. It is particularly preferable to use one or more selected from the group consisting of ethyl (meth) acrylate, butyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
- the mass ratio of them ([the alkyl group having 1 to 10 carbon atoms) (Meth) acrylic acid alkyl ester] / [hydroxyl-containing (meth) acrylate]) is in the range of 99.1 / 0.9 to 99.9 / 0.1 such as drop impact resistance It is preferable from the viewpoint.
- the number average molecular weight of the acrylic resin (iii) is preferably from 1,000 to 200,000, particularly preferably from 1,000 to 100,000, from the viewpoint of improving drop impact resistance and the like.
- the number average molecular weight of the (meth) acrylic resin (iii) 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 resin (iii) is preferably in the range of 0 ° C. or less, more preferably in the range of 0 to ⁇ 80 ° C., and in the range of ⁇ 10 to ⁇ 50 ° C. from the viewpoint of improving the drop impact resistance and the like. A range is more preferred.
- the glass transition temperature of the (meth) acrylic resin (iii) 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 resin (iii) used is preferably in the range of 0.5 to 50 parts by mass with respect to 100 parts by mass of the polyol (A) from the viewpoint of further improving the drop impact resistance and the like.
- the range of 30 parts by mass is more preferable, and the range of 2 to 20 parts by mass is still more preferable.
- the prepolymer (i) can be added and mixed after the prepolymer (i) is produced, or the polyol (A) can be produced when the prepolymer (i) is produced. Then, the polyisocyanate (B) may be supplied and reacted.
- the acrylic resin When the moisture curable polyurethane hot melt resin composition of the present invention imparts only two components of the urethane prepolymer (i) and the curing catalyst (ii), or when giving drop impact resistance, the acrylic resin ( It may be composed of only three components added with iii), 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, fast curable, flexible, adhesive to various substrates, application workability, and maintenance after application. It is excellent in moldability 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, PC (polycarbonate), PBT (polybutylene terephthalate), modified PPE (polyphenylene ether) ), PEN (polyethylene naphthalate), PET (polyethylene terephthalate), lactic acid polymer, ABS resin, AS resin and the like can be used. 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-2 (reaction of 1,6-hexanediol and 1,12-dodecanedicarboxylic acid, number average molecular weight; 3,500) 20 parts by mass, amorphous PEs-1 (reaction of 6 mol adduct of bisphenol A with propylene oxide, sebacic acid and isophthalic acid, number average molecular weight; 2,000) 7.5 parts by mass Amorphous PEs-2 (reacted with neopentyl glycol, diethylene glycol, 1,6-hexan
- Examples 2 to 7, Comparative Examples 1 to 6 Moisture curable polyurethane hot melt resin composition as in Example 1 except that the type and / or amount of polyol, the amount of polyisocyanate, and the type and / or amount of curing catalyst were changed as shown in Tables 1-2. I got a thing.
- Moisture curable polyurethane hot melt resin compositions obtained in Examples and Comparative Examples were melted to 120 ° C. and dispensed with a 0.6 mm inner diameter dispenser needle (“VALVE MASTER ME-5000VT”, Musashi Engineering, preheated to 120 ° C.
- the coating workability was judged as follows based on the coating amount (g) when ejected for 10 seconds at a discharge pressure of 0.3 MPa and a speed of 50 mm / sec.
- coating was judged as follows by the height (mm) of the adhesive bond layer immediately after apply
- the moisture curable polyurethane hot melt resin compositions of Examples 1 to 7 of the present invention are waterproof, fast curable, flexible, adhesive to various substrates, application workability, and shape retention after application. It was found to be excellent in performance and open time.
- Comparative Examples 1 and 7 were embodiments that did not contain the polyether polyol (A-1), but were found to have poor waterproofness, adhesiveness, and the like.
- Comparative Examples 2 and 8 were embodiments that did not contain the crystalline polyester polyol (A-2), but were found to have poor waterproofness, open time, adhesion, and the like.
- Comparative Examples 3 and 9 were embodiments that did not contain the amorphous polyester polyol (A-3), but were found to have poor waterproofness, flexibility, adhesion, and the like.
- Comparative Examples 4 and 10 were embodiments that did not contain acrylic polyol (A-4), but were found to be poor in waterproofness, adhesiveness, open time, and the like.
- Comparative Examples 5 and 11 are embodiments in which dibutyltin dilaurate, which is a metal catalyst, is used as a curing catalyst, but gelation has occurred.
- Comparative Examples 6 and 12 are embodiments using trioctylamine as a tertiary amine catalyst as a curing catalyst, but foamed and gelled.
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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、速硬化を望む場面では実用上使用できないものであり、またエポキシ樹脂を用いているため、接着剤自体の柔軟性も不十分であり、使用できる用途が限られているとの問題点があった。
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、メタクリル酸340質量部、メタクリル酸ブチル340質量部、メタクリル酸2-ヒドロキシエチル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;20,000mPa・s(23℃))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-2(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)20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)7.5質量部、非晶性PEs-2(ネオペンチルグリコール、ジエチレングリコール、1,6-ヘキサンジオール及びアジピン酸を反応させたもの、数平均分子量;2,000)7.5質量部、アクリルポリオール-1を20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。
次いで、該ウレタンプレポリマーに、ビス(2,6-ジメチルモルホリノエチル)エーテルを0.1質量部加えて、湿気硬化型ポリウレタンホットメルト樹脂組成物を得た。
ポリオールの種類及び/又は量、ポリイソシアネートの量、硬化触媒の種類及び/又は量を表1~2に示す通りに変更した以外は、実施例1と同様にして湿気硬化型ポリウレタンホットメルト樹脂組成物を得た。
実施例及び比較例で得られた湿気硬化型ポリウレタンホットメルト樹脂組成物を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(「VALVE MASTER ME-5000VT」、武蔵エンジニアリング製)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、以下のように判断した。なお、硬化触媒を入れた直後に樹脂組成物がゲル化したものは、以降の評価は行わず、表中では「-」とした。
<塗布作業性>
「A」;0.25g以上0.5g未満
「B」;0.1g以上0.25g未満
「C」;0.1g未満
<塗布後の保型性>
「A」;0.36mm以上
「B」;0.24mm以上0.36mm未満
「C」;0.24mm未満
<オープンタイム>
「Y」;4分以上10分未満
「N」;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。
「A」;6.0MPa未満
「B」;6.0MPa以上10.0MPa未満
「C」;10.0MPa以上
実施例及び比較例で得られた湿気硬化型ポリウレタンホットメルト樹脂組成物を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(アクリロニトリル・ブタジエン・スチレン共重合樹脂(ABS)板、ポリカーボネート(PC)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湿気硬化型ポリウレタンホットメルト樹脂組成物を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、次いで前記と同じPETを貼り合せた。該貼り合せから3分後に、30℃雰囲気下で該PETに1kgの荷重を90°方向に与え、1時間ごとに経時の剥離の有無を確認した。なお、剥離が確認できなかった場合は「Y」、確認できた場合は「N」と評価した。
実施例及び比較例で得られた湿気硬化型ポリウレタンホットメルト樹脂組成物を120℃に溶融し、120℃に予め加熱された内径0.6mmのディスペンサーニードル(「VALVE MASTER ME-5000VT」、武蔵エンジニアリング製)を用いて吐出圧力:0.3MPa、速度:50mm/秒にて、PC板(5cm×5cm)の型枠に正方形状に塗布して、次いで、ABS板を貼り合せ、物品を得た。該物品を水浸漬(23℃、0.5時間)させた後、物品内部への水の侵入の有無を、JIS IPX-7に準拠して行い、以下のように判断した。
「Y」;水の侵入がない。
「N」;水の侵入がある。
「結晶性PEs-1」;1,6-ヘキサンジオールとアジピン酸を反応させたもの、数へ金分子量;2,000
「非晶性PEs-2」;ネオペンチルグリコール、ジエチレングリコール、1,6-ヘキサンジオール及びアジピン酸を反応させたもの、数平均分子量;2,000)
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、PPG1000を15質量部、PPG2000を15質量部、結晶性PEs-1を10質量部、結晶性PEs-2を10質量部、非晶性PEs-1を15質量部、アクリルポリオール-1を20質量部、(メタ)アクリル樹脂-1([アクリル酸ブチル/メタクリル酸ブチル/アクリル酸エチル/メタクリル酸2-ヒドロキシエチル]=69.65/25/5/0.35(質量比)で反応させたもの、数平均分子量13,000、ガラス転移温度;-30.3℃)2.5質量部を仕込み、減圧条件下で水分含有率が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)16.5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。
次いで、該ウレタンプレポリマーに、ビス(2,6-ジメチルモルホリノエチル)エーテルを0.1質量部加えて、湿気硬化型ポリウレタンホットメルト樹脂組成物を得た。
ポリオールの種類及び/又は量、ポリイソシアネートの量、硬化触媒の種類及び/又は量を表3~5に示す通りに変更した以外は、実施例8と同様にして湿気硬化型ポリウレタンホットメルト樹脂組成物を得た。
実施例及び比較例で得られた湿気硬化型ポリウレタンホットメルト樹脂組成物を120℃に溶融し、120℃に予め加熱された内径0.6mmのディスペンサーニードル(「VALVE MASTER ME-5000VT」、武蔵エンジニアリング製)を用いて吐出圧力:0.3MPa、速度:50mm/秒にて、PC板(5cm×5cm)上に、4cm×4cmの正方形を描くように塗布して、次いで、ABS板を貼り合せ、23℃、65%RHの条件下で3日間放置した。
次いで、デュポン式落下衝撃試験機にてABS板から撃芯を介して、荷重:300g、高さ:30cmで衝撃を5回与える条件にて、PC板の剥がれの発生の有無を目視観察し、以下のように判断した。
「Y」:剥がれが発生しなかった。
「N」:剥がれが発生していた。
「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
「(メタ)アクリル樹脂-2」;[アクリル酸ブチル/メタクリル酸ブチル/メタクリル酸2-ヒドロキシエチル=74.65/25/0.35(質量比)で反応させたもの、ガラス転移温度;-31℃]
「(メタ)アクリル樹脂-3」;[アクリル酸ブチル/メタクリル酸ブチル]=75/25で反応させたもの、ガラス転移温度;-31.6℃
Claims (12)
- 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、5~150℃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。
- 前記硬化触媒(ii)が、ジモルホリノジエチルエーテル及びビス(2,6-ジメチルモルホリノエチル)エーテルからなる群より選ばれる1種以上のものである請求項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。
- 前記硬化触媒(ii)の使用量が、前記ウレタンプレポリマー(i)100質量部に対して、0.05~5.0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。
- アクリル樹脂(iii)を更に含有す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。
- 前記アクリル樹脂(iii)のガラス転移温度が、0℃以下である請求項8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。
- 前記アクリル樹脂(iii)の使用量が、前記ポリオール(A)100質量部に対して、0.5~50質量部の範囲である請求項8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1~10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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TW201345939A (zh) | 2013-11-16 |
KR20140107470A (ko) | 2014-09-04 |
TWI570145B (zh) | 2017-02-11 |
US20150099125A1 (en) | 2015-04-09 |
MY167922A (en) | 2018-09-28 |
JPWO2013153907A1 (ja) | 2015-12-17 |
KR101691870B1 (ko) | 2017-01-03 |
JP5360516B1 (ja) | 2013-12-04 |
US9464155B2 (en) | 2016-10-11 |
CN104245769B (zh) | 2016-08-17 |
CN104245769A (zh) | 2014-12-24 |
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