TW201510072A - Moisture-curable hot melt urethane composition and adhesive - Google Patents

Abstract

The present invention addresses the problem of providing a moisture-curable hot melt urethane composition from which an adhesive having excellent adhesion and detachability can be obtained. The present invention provides the moisture-curable hot melt urethane composition which comprises an urethane prepolymer (A) having an isocyanate group and an acrylic polymer (B). The present invention also provides an adhesive which is obtained using the moisture-curable hot melt urethane composition. The content of the acrylic polymer (B) is preferably in a range of 1 to 100 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A). This moisture-curable hot melt urethane composition provides an adhesive having excellent adhesion and detachability and thus, the composition not only can be used for bonding fiber and laminating building materials but can also be suitably used for bonding optical components.

Description

Moisture-curing hot-melt urethane composition and adhesive

The present invention relates to a moisture-curing hot-melt urethane composition which is an adhesive which can provide superior adhesion and releasability.

Since the adhesive obtained by using the moisture-curing type hot-melt urethane composition is solvent-free, as an environmentally-compatible adhesive, various studies centering on fiber bonding/layer building materials have been performed. It is also widely used in the industry.

In addition, in recent years, the bonding of optical members has been demanded to reduce the weight and thickness of optical members, and the use of alternative hot-melt urethane adhesives has been pursued as an acrylic adhesive which has hitherto been the mainstream.

As the adhesive, for example, an adhesive using a composition resistant to moist heat and hot melt adhesive has been disclosed, which is characterized by a polyurethane having a flow initiation temperature of 55 ° C or more and 110 ° C or less with respect to (a) a flow initiation temperature of 55 ° C or more and 110 ° C or less. 100 parts by weight of the resin, blending: (b) 5 to 150 parts by weight of a saturated polyester resin having a Tg of 0 ° C or more and 110 ° C or less and a molecular weight of 10,000 to 25,000; (c) a softening point of 60 ° C or more and 140 ° C or less, 10 to 150 parts by weight of the epoxy resin having a molecular weight of 700 to 3,000; and (d) 10 to 200 parts by weight of the inorganic filler surface-treated with a coupling agent (for example, refer to Patent Document 1).

Since the laminated system obtained by using the adhesive has a strong adhesive strength, it has an advantageous effect from the viewpoint of adhesion. However, since the back side peeling cannot be performed, there is a problem that reworkability is deteriorated. In particular, in recent years, the use of a moisture-curable hot-melt urethane composition for use in an optical member has been increased, and a high-priced substrate such as a display portion or a frame of a liquid crystal panel is often used, and improvement is strongly sought. Substrate reworkability due to adhesion of the adhesive.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2003-27030

An object of the present invention is to provide a moisture-curing hot-melt urethane composition which can provide an excellent adhesiveness and releasability.

The inventors of the present invention have conducted research in order to solve the problem, and have focused on the use of a plasticizer, and have completed the present invention.

That is, the present invention provides a moisture-curing hot-melt urethane composition containing a urethane prepolymer (A) having an isocyanate group and an acrylic polymer (B).

The adhesive containing the moisture-curing hot-melt urethane composition of the present invention is excellent in adhesion, and can be heated by heating or the like. Easy to peel off. Therefore, the reworkability due to the peeling of the adhesive is also excellent.

[Formation of the Invention]

The moisture-curing hot-melt urethane composition of the present invention contains a urethane prepolymer (A) having an isocyanate group (hereinafter, simply referred to as a urethane prepolymer (A). )") and acrylic polymer (B).

As the urethane prepolymer (A), for example, a polyol obtained by reacting a polyhydric alcohol with a polyisocyanate can be used.

As the polyol, a polyether polyol, a crystalline polyester polyol, a non-crystalline polyester polyol, an acrylic polyol, a polycarbonate polyol, a polybutadiene polyol, a dimer diol can be used. Wait. These polyols may be used alone or in combination of two or more. When the moisture-curable hot-melt urethane composition is used in the bonding of the optical member, the polyol can be excellent in water repellency, rapid hardenability, flexibility, adhesion, and coating. The workability and the shape retention property after application impart an adhesive to the adhesive, preferably containing a polyether polyol, a crystalline polyester polyol, a non-crystalline polyester polyol, an acrylic polyol, and a polycarbonate polyol. At least one or more polyols of the group formed by the alcohol.

The polyether polyol preferably imparts superior melt viscosity, break time (time to fit), adhesion, water repellency, flexibility, and For impact resistance, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol, ethylene oxide modified polypropylene glycol, or the like can be used. These polyether polyols may be used alone or in combination of two or more.

The number average molecular weight of the polyether polyol is preferably in the range of 500 to 5,000, from the viewpoint of imparting superior adhesion (particularly, initial bonding strength and final bonding strength) and a moderate breaking time after coating. Good range from 700 to 5,000. Further, the number average molecular weight of the polyether polyol means a value measured by a gel permeation chromatography (GPC) method using the following conditions.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)

Column: The following columns made of Tosoh Co., Ltd. are connected in series and used.

"TSKgel G5000" (7.8mm I.D.×30cm) × 1

"TSKgel G4000" (7.8mm I.D.×30cm) × 1

"TSKgel G3000" (7.8mm I.D.×30cm) × 1

"TSKgel G2000" (7.8mm I.D.×30cm) × 1

Detector: RI (differential refractometer)

Column temperature: 40 ° C

Eluent: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

Injection amount: 100 μL (sample concentration 0.4% by mass in tetrahydrofuran solution)

Standard sample: A calibration curve is prepared using the following standard polystyrene. (standard polystyrene)

"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Co., Ltd.

From the viewpoint of imparting superior adhesion (especially initial adhesion strength and final adhesion strength) and moderate disconnection time after coating The amount used in the case of using the polyether polyol is preferably in the range of 5 to 60% by mass in the polyol.

The crystalline polyester polyol preferably imparts excellent water repellency, adhesion (especially initial adhesion strength), breaking time, and drop impact resistance. For example, a reaction product of a compound having a hydroxyl group and a polybasic acid can be used. In the present invention, the crystallinity is based on the DSC (slight differential calorimeter) measurement according to JIS K 7121:2012, and indicates that the peak of crystallization heat or heat of fusion can be confirmed. The peak cannot be confirmed.

As the compound having a hydroxyl group, for example, ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, heptanediol, octanediol, decanediol, decanediol, trimethylolpropane can be used. , trimethylolethane, glycerin, and the like. These compounds may be used alone or in combination of two or more. Among these, butanediol, hexanediol, octanediol, and decanediol are preferably used from the viewpoint of improving crystallinity and improving water repellency and adhesion.

As the polybasic acid, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, 1,12-dodecanedicarboxylic acid or the like can be used. These polybasic acids may be used singly or in combination of two or more.

The number average molecular weight of the crystalline polyester polyol is preferably in the range of from 500 to 5,000, more preferably in the range of from 1,000 to 4,000, from the viewpoint of water repellency and adhesion. Further, the number average molecular weight of the crystalline polyester polyol means a value measured in the same manner as the number average molecular weight of the polyether polyol.

Further, from the viewpoint of water repellency and adhesion, the glass transition temperature (Tg) of the crystalline polyester polyol is preferably 40 to 130 ° C. The scope. Further, the glass transition temperature of the crystalline polyester polyol means a value measured by DSC in accordance with JIS K 7121:2012, specifically, it means that the crystalline polyester polyol is placed in a fine range. In the scanning calorimeter device, after raising the temperature to (Tg + 50 ° C) at 10 ° C / min, the temperature was rapidly maintained for 3 minutes, and the intermediate point glass transition temperature (Tmg) read from the obtained differential thermal curve was performed.

The amount of the crystalline polyester polyol to be used is preferably from 5 to 50% by mass in the polyol, from the viewpoints of flexibility, adhesion, and breaking time.

Further, as the crystalline polyester polyol, a polycaprolactone polyol can also be used. As the polycaprolactone polyol, for example, a compound having a hydroxyl group and ε-caprolactone can be used.

Further, in the case of using a polycaprolactone polyol as the crystalline polyester polyol, the number average molecular weight is preferably in the range of 20,000 to 200,000.

The amorphous polyester polyol preferably provides a superior breaking time (adhesive time), adhesion, water repellency, flexibility, and drop impact resistance. For example, the following compounds having a hydroxyl group and a polybasic acid can be used. Reactant.

The compound having a hydroxyl group, for example, 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 or bisphenol F, and epoxide addition products thereof. These compounds may be used alone or in combination of two or more. Among these, the water resistance, adhesion, flexibility and resistance can be further improved. From the standpoint of impact, it is preferred to use an epoxide adduct of bisphenol A. Further, the number of addition moles of the epoxide is preferably in the range of 2 to 10 moles, more preferably in the range of 4 to 8 moles.

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, and the like. These polybasic acids may be used singly or in combination of two or more.

The number average molecular weight of the amorphous polyester polyol is preferably in the range of 500 to 5,000, more preferably in the range of 1,000 to 4,000, still more preferably 1,000 to 3,000, from the viewpoints of water repellency, adhesion and flexibility. The scope. The number average molecular weight of the amorphous polyester polyol is a value measured in the same manner as the number average molecular weight of the polyether polyol.

The glass transition temperature of the amorphous polyester polyol is preferably in the range of -70 to -10 ° C from the viewpoints of water repellency, adhesion and flexibility. Further, the glass transition temperature of the amorphous polyester polyol is the same as the method for measuring the glass transition temperature (Tg) of the crystalline polyester polyol.

From the viewpoint of water repellency, adhesion, and flexibility, the amount of the amorphous polyester polyol used is preferably in the range of 3 to 50% by mass in the polyol.

The acrylic polyol preferably has a moderate breaking time (time to bond), water repellency, adhesion, and drop impact resistance, and the polymerization is carried out by using a (meth)acrylic compound having a hydroxyl group as an essential component. The (meth)acrylic compound obtained. In the present invention, the "(meth)acrylic compound" means either or both of a methacrylic compound and an acrylic compound.

As the (meth)acrylic compound having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate can be used. Ester and the like. These compounds may be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferably used from the viewpoint of availability.

As other usable (meth)acrylic compounds, for example, (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (a) Isobutyl acrylate, tert-butyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, (methyl) ) stearyl acrylate, isostearyl (meth) acrylate, hexadecyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate-2, 2,2-trifluoroethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, -1H,1H,5H-octafluoropentyl ester, (meth)acrylic acid -2-(perfluorooctyl)ethyl ester, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, polyethylene glycol- Methyl)acrylate, methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, polyethylene glycol (methyl) Methoxy acrylate, benzyl (meth) acrylate, 2-ethyl-2-methyl-(meth)acrylate-[1,3 ]-Dioxolane-4-ylmethyl ester, dimethylaminoethyl (meth)acrylate, isodecyl (meth)acrylate, and the like. These The acrylic compound may be used singly or in combination of two or more. Among these, (meth) acrylate having an alkyl group having a carbon number of 1 to 10 is preferably used from the viewpoint of further improving water repellency, adhesion, breaking time, and drop impact resistance. Particularly preferred is methyl (meth)acrylate or n-butyl (meth)acrylate.

In the case of using the (meth) acrylate having an alkyl group having a carbon number of from 1 to 10, from the viewpoints of water repellency, adhesion, breaking time, and drop impact resistance, the number of carbon atoms a mass ratio of the alkyl (meth) acrylate of the alkyl group to the (meth) acrylate having a hydroxyl group in the range of 1 to 10, ([(meth)acrylic acid having an alkyl group having a carbon number of 1 to 10) The ester]/[(meth)acrylate having a hydroxyl group]) is preferably in the range of from 90/10 to 99/1.

The acrylic polyol preferably has a number average molecular weight of from 5,000 to 50,000, particularly preferably from 10,000 to 30,000, from the viewpoint of further improving water repellency, adhesion, and breaking time. Further, the number average molecular weight of the acrylic polyol is the same as the method for determining the number average molecular weight of the polyether polyol.

The glass transition temperature of the acrylic polyol is preferably in the range of 5 to 150 ° C, more preferably in the range of 30 to 120 ° C, from the viewpoints of water repellency, adhesion (especially initial adhesion strength), and breaking time. It is preferably in the range of 50 to 80 °C. Further, the glass transition temperature of the acrylic polyol is the same as the method for measuring the glass transition temperature (Tg) of the crystalline polyester polyol.

From the viewpoints of water repellency, adhesion, and breaking time, the amount of the acrylic polyol used is preferably in the range of 0.5 to 20% by mass in the polyol.

As the polycarbonate polyol, for example, a carbonate and/or phosgene can be used, and a compound obtained by reacting the above compound having a hydroxyl group can be used.

As the carbonate, for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate, diphenyl carbonate or the like can be used. These compounds may be used alone or in combination of two or more.

From the viewpoint of adhesion, the number average molecular weight of the polycarbonate polyol is preferably in the range of 500 to 5,000, more preferably in the range of 1,000 to 4,000. Further, the number average molecular weight of the polycarbonate polyol means a value measured in the same manner as the number average molecular weight of the polyether polyol.

The glass transition temperature of the polycarbonate polyol is preferably in the range of -30 to 20 ° C from the viewpoint of further improving the impact resistance and adhesion. Further, the glass transition temperature of the polycarbonate polyol is the same as the method for measuring the glass transition temperature (Tg) of the crystalline polyester polyol.

From the viewpoint of further improving the impact resistance and adhesion, the amount of the polycarbonate polyol used is preferably in the range of 5 to 85% by mass in the polyol.

As the polyisocyanate, for example, polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, phenyl diisocyanate, toluene diisocyanate, or the like can be used. An aromatic polyisocyanate such as naphthalene diisocyanate; hexamethylene diisocyanate, diazonic acid diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate An aliphatic or alicyclic polyisocyanate such as an acid ester, xylene diisocyanate or tetramethyl xylene diisocyanate. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanate is preferably used from the viewpoints of reactivity, adhesion, and impact resistance, and diphenylmethane diisocyanate and xylene diisocyanate are more preferably used.

The urethane prepolymer (A) is preferably obtained by reacting the polyol with the isocyanate, having a prepolymerizable in the polymer terminal or molecule with air or in the presence of a urethane coating. The moisture of the substrate of the substance reacts to form an isocyanate group of a crosslinked structure.

As a method for producing the urethane prepolymer (A), for example, by heating a mixture of the polyol in a reaction container to which the polyisocyanate has been added, it is heated. A method in which a hydroxyl group of the polyol is produced by reacting an isocyanate group of the polyisocyanate under an excessive condition.

In the production of the urethane prepolymer (A), the isocyanate group of the polyisocyanate and the hydroxyl group of the polyol are from the viewpoints of water repellency, adhesion, flexibility, and drop impact resistance. The equivalent ratio ([isocyanate group/hydroxy group]) is preferably in the range of 1.1 to 5, more preferably in the range of 1.5 to 3.

In the production of the urethane prepolymer (A), a urethane catalyst can be used as necessary. The urethane catalyst can be suitably added at any stage of the reaction.

The urethane catalyst can use, for example, triethylamine, triethylenediamine, and N-methyl. a nitrogen-containing compound such as a phenyl group; a metal salt such as potassium acetate, zinc stearate or tin octylate; an organometallic compound such as dibutyltin dilaurate or the like. These catalysts may be used alone or in combination of two or more.

The isocyanate group content (hereinafter, abbreviated as "NCO%") of the urethane prepolymer (A) obtained by the above method, from the viewpoint of further improving the water repellency, the adhesion, and the flexibility. It is preferably in the range of 1.5 to 8.0%, more preferably in the range of 1.7 to 5.0%, particularly preferably in the range of 1.8 to 3.0%. Further, the NCO% of the urethane prepolymer is a value measured by a potentiometric titration method in accordance with JIS K 1603-1:2007.

As the viscosity of the urethane prepolymer (A), the melt viscosity at 125 ° C is preferably from 1,000 to 50,000 mPa from the viewpoint of workability and adhesion. The range of s is more preferably 2,000 to 10,000 mPa. The range of s. Further, the melt viscosity at 125 ° C indicates a value measured by an ICI Cone Plate viscometer.

The softening point of the urethane prepolymer (A) is preferably in the range of 30 to 120 ° C from the viewpoints of water repellency, adhesion, workability, and drop impact resistance. In addition, the softening point refers to a temperature at which the heat flow starts to lose the cohesive force in the case where the temperature of the urethane prepolymer (A) is gradually increased. Further, the softening point of the urethane prepolymer (A) means a value obtained by a ring and ball according to JIS K 5902-1969.

In order to solve the problem of the present invention, it is necessary to use an acrylic polymer as the acrylic polymer (B). The acrylic polymer (B) functions as a plasticizer and does not cause a moisture-curable hot-melt amine group. The viscosity and cohesive force of the formate composition and other physical properties necessary as an adhesive are lowered to improve adhesion and peelability. Further, as a method of peeling off the substrate to be described later and the moisture-curing hot-melt adhesive layer of the present invention, a method of using a release agent is also considered, in which the laminate is heated to accelerate the peeling, because It is not good to consider the adverse effects of the release agent on the human body.

From the viewpoints of adhesion, releasability, and compatibility with the urethane prepolymer (A), as the acrylic polymer (B), for example, it is preferred to use an alkyl (meth)acrylate as a necessity. A component obtained by polymerizing a (meth)acrylic compound.

As the (meth)acrylic acid alkyl ester, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (A) can be used. Base) tert-butyl acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, stearyl (meth)acrylate, (methyl) Isostearyl acrylate, 2-ethylhexyl (meth)acrylate, hexadecyl (meth)acrylate, lauryl (meth)acrylate, and the like. These compounds may be used alone or in combination of two or more.

In addition to the (meth)acrylic acid alkyl ester, as the (meth)acrylic compound which can be used, for example, (meth)acrylic acid-2,2,2-trifluoroethyl ester or (meth)acrylic acid can be used. 2,2,3,3-tetrafluoropropyl ester, (meth)acrylic acid-1H, 1H, 5H-octafluoropentyl ester, (meth)acrylic acid-2-(perfluorooctyl)ethyl ester, etc. a (meth)acrylic compound having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or hydroxybutyl (meth)acrylate; (A a lipid such as isodecyl acrylate, cyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate or the like Cyclic (meth)acrylic compound; polyethylene glycol mono(meth)acrylate, methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, methoxytriethyl (meth)acrylate (meth)acrylic acid compound having an ether group such as a glycol ester or a polyethylene glycol (meth) acrylate; (benzyl) methacrylate, 2-ethyl-2-(meth)acrylate Methyl-[1,3]-dioxolan-4-ylmethyl ester, dimethylaminoethyl (meth)acrylate, and the like. These compounds may be used alone or in combination of two or more.

The weight average molecular weight of the acrylic polymer (B) is preferably in the range of 1,000 to 10,000, more preferably in the range of 1,500 to 8,000, from the viewpoint of further improving the adhesion and the releasability. Further, the method for measuring the weight average molecular weight of the acrylic polymer (B) is the same as the method for measuring the number average molecular weight of the polyether polyol.

The glass transition temperature of the acrylic polymer (B) is preferably -10 ° C or lower, more preferably -20 to -100 ° C, more preferably from the viewpoint of further improving the adhesion and the releasability. -25 to -85 ° C range. Further, the method for measuring the glass transition temperature of the acrylic polymer (B) is the same as the method for measuring the glass transition temperature (Tg) of the polyether polyol.

The content of the acrylic polymer (B) is preferably in the range of 1 to 100 parts by mass based on 100 parts by mass of the urethane prepolymer (A) from the viewpoint of adhesion and releasability. More preferably, it is in the range of 3 to 70 parts by mass, further preferably in the range of 10 to 80 parts by mass, particularly preferably in the range of 25 to 70 parts by mass.

The moisture-curing hot-melt urethane composition of the present invention contains the urethane prepolymer (A) and the acrylic polymer (B) as essential components, and may contain other additives as necessary. .

As such other additives, for example, a curing catalyst, an antioxidant, an adhesion-imparting agent, a stabilizer, a filler, a dye, a pigment, a decane coupling agent, a wax, or the like can be used. These additives may be used alone or in combination of two or more.

As the hardening catalyst, for example, dimethyltin oxide, dibutyltin oxide, monobutyltin oxide, dioctyltin oxide, diphenyltin oxide, dibutyltin dioctoate, dibutyltin distearate, and bis (which can be used) can be used. 2-ethylhexanoic acid) dibutyltin, tributyltin stearate, tripropyltin stearate, triphenyltin stearate, tetraphenyltin, dibutyltin-3-mercaptopropionate, dioctyl a tin compound such as tin-3-mercaptopropionate or dibutyltin maleate polymer; acetonitrile, isopropyl aluminum oxide, aluminum stearate, aluminum 2-ethylhexanoate, acetaminoacetic acid Aluminum compound such as aluminum, tris(acetic acid) aluminum, tris(ethylacetylacetic acid) aluminum, hexafluoroacetic acid aluminum or the like; tetramethoxy titanium, tetraethoxy titanium, tetrastearyl oxygen Titanium compound such as titanium, hydroxystearyl titanium, isopropoxy stearyl titanium, poly(ethionyltitanate), poly(hydroxystearate), etc.; zirconia, zirconium isopropoxide, hard Zirconium compound such as zirconium strontium sulphate, zirconium octoate octoate, zirconium acetylate acetate, zirconium trifluoroacetate, etc.; Polinyl diethyl ether, bis(2,6-dimethyl Polinylethyl)ether A porphyrin compound or the like. These hardening catalysts may be used alone or in combination of two or more. Among these, from the viewpoint of maintaining water repellency, flexibility, and adhesion while further improving rapid hardenability, it is preferably used. Porphyrin compound, better use two Diethyl ether, bis(2,6-dimethyl Polinylethyl)ether.

From the viewpoint of rapid hardenability and manufacturing stability, the amount of the curing catalyst is preferably from 0.05 to 5.0 parts by mass based on 100 parts by mass of the urethane prepolymer (A). More preferably, it is in the range of 0.05 to 2.0 parts by mass.

The moisture-curing hot-melt urethane composition of the present invention is an adhesive which imparts excellent adhesion and releasability, and can be applied not only to fiber bonding/deposition of building materials but also to bonding of optical members.

Examples of the form of bonding to the optical member include a sealant such as a mobile phone, a personal computer, a game machine, a car navigation, a camera speaker, and an electric axis of a fishing tackle.

In the case of performing the bonding, for example, the moisture-curable hot-melt urethane composition is heated and melted in a temperature range of 50 to 130 ° C, and the composition is applied to one side. On the substrate, a method of bonding a substrate on the other side to the resin layer to obtain a laminate is obtained.

As the substrate, for example, a metal plate such as a glass plate, stainless steel (SUS), magnesium, or aluminum; a cycloolefin resin such as norbornene; an acrylic resin, a urethane resin, an anthracene resin, or an epoxy resin can be used. Resin, fluororesin, polystyrene resin, polyester resin, polyfluorene resin, polyarylate resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyolefin resin, polyimine resin, alicyclic polymer Amine resin, polyamide resin, cellulose resin, polycarbonate (PC), polybutylene terephthalate (PBT), polyphenylene ether (modified PPE), polyethylene naphthalate (PEN) Plastic substrate of polyethylene terephthalate (PET), lactic acid polymer, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), etc. Wait. Further, these substrates may be subjected to corona treatment, plasma treatment, primer treatment, and the like as necessary. Moreover, these base materials may be used alone or in combination of two or more.

As a method of applying the moisture-curing hot-melt urethane composition to the substrate, for example, a roll coater, a spray coater, a T-die coater, a knife coater, and a teasing machine can be used. Point coater, etc. Further, since the moisture-curable hot-melt urethane composition has low viscosity and shape retention, it can be coated by a dispenser, inkjet printing, screen printing, offset printing or the like. . According to these coating methods, since the moisture-curable hot-melt urethane composition can be applied to the substrate to be coated, the loss of penetration processing or the like does not occur. Preferably. Further, according to the coating method, the moisture-curable hot-melt urethane composition can be formed into a dot shape, a linear shape, a triangular shape, or a square shape continuously or intermittently on the substrate. Various shapes such as round shapes and curves.

The thickness of the adhesive layer using the moisture-curable hot-melt urethane composition can be set according to the use to be used, and for example, it can be preferably set in the range of 10 μm to 5 mm.

The maturing conditions after the bonding can be appropriately determined, for example, at a temperature of 20 to 80 ° C, a humidity of 50 to 90%, and a period of 0.5 to 5 days.

By the above method, a laminate having the firmly adhered base material layer and the moisture-curable hot-melt urethane adhesive layer can be obtained. As a method of removing the moisture-curable hot-melt urethane adhesive layer from the laminate, the substrate is recovered, and for example, a method of heating the laminate in a range of 40 to 150 ° C is preferred.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples.

[Synthesis Example 1] <Synthesis of urethane prepolymer (A-1)>

15 parts by mass of polypropylene glycol (number average molecular weight: 1,000) and 15 parts by mass of polypropylene glycol (number average molecular weight: 2,000), 10 were added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. Parts by mass of crystalline polyester polyol-1 (reacted with 1,6-hexanediol and adipic acid, number average molecular weight: 2,000), and 10 parts by mass of crystalline polyester polyol-2 (1) , 6-hexanediol reacted with 1,12-dodecanedicarboxylic acid, number average molecular weight: 3,500), 15 parts by mass of amorphous polyester polyol-1 (propylene oxide of bisphenol A) 6 molar addition, azelaic acid and terephthalic acid reaction, number average molecular weight: 2,000), 2.5 parts by mass of acrylic polyol-1 (butyl acrylate / methyl methacrylate / ethyl acrylate / 2-hydroxyethyl methacrylate=69.65/25/5/0.35 (mass ratio) reaction product, number average molecular weight: 13,000, glass transition temperature: -30.3 ° C), dehydrated under reduced pressure until moisture The content ratio is 0.05% by mass or less.

Then, after cooling to a temperature of 70 ° C in the vessel, 16.5 parts by mass of 4,4'-diphenylmethane diisocyanate was added, and the temperature was raised to 100 ° C until the isocyanate group content was kept constant for about 3 hours. A urethane prepolymer (A-1) having an isocyanate group.

[Synthesis Example 2]

60 parts by mass of polycarbonate is added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux cooler. Polyol (Duranol T4672, manufactured by Asahi Kasei Chemicals Co., Ltd., number average molecular weight: 2,000, Tmg: 10 ° C), 10 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000), 15 parts by mass of crystal PEs-1 (reaction of 1,6-hexanediol with sebacic acid, Tmg: 65 ° C, number average molecular weight: 3,500), dehydration under reduced pressure at 100 ° C until the moisture content becomes 0.05 mass %the following.

Then, after cooling to a temperature of 70 ° C in the vessel, 13.2 parts by mass of xylene diisocyanate and 0.03 parts by mass of tin octylate were added, and the temperature was raised to 100 ° C until the NCO group content became constant, and the reaction was allowed to proceed for about 3 hours. A urethane prepolymer (A-2) having an isocyanate group.

[Example 1] Preparation of moisture-curing hot-melt urethane composition

To 100 parts by mass of the urethane prepolymer (A-1) obtained in Synthesis Example 1, 50 parts by mass of an acrylic plasticizer was added: "ARUFON (registered trademark) UP-1010, manufactured by Toagosei Co., Ltd. (weight average molecular weight: 1,700, Tg: -31 ° C), a moisture-curing hot-melt urethane composition was obtained.

[Examples 2 to 9, Comparative Examples 1 to 3]

A moisture-curing hot-melt urethane composition was obtained in the same manner as in Example 1 except that the types and/or amounts of the component (A) and the component (B) used were changed as shown in Table 1. . Further, if the compatibility of the urethane prepolymer and the plasticizer is poor and the laminate cannot be obtained, the evaluation is evaluated as "-" without the following evaluation.

[Production of laminated body]

The moisture-curable hot-melt urethane composition obtained in the examples and the comparative examples was heated to 110 ° C to be melted, and the use was added. Dispenser needle (VAVE MASTER ME-5000VT, manufactured by Musashi Engineering Co., Ltd.) having a diameter of 0.4 mm and having a diameter of 0.4 mm, which is heated to 110 ° C, with a discharge pressure of 0.3 MPa and a processing speed of 60 mm / sec. The part was coated on a ABS plate (7 cm × 7 cm) having a diameter of 1 cm and coated with a square of 4 cm on one side to have a thickness of 0.2 mm, and the acrylic plate (5 cm × 5 cm) was attached thereto. The laminate was placed in a constant temperature and humidity chamber at a temperature of 23 ° C and a humidity of 65% for 3 days to obtain a laminate.

[Method of evaluation of adhesion]

Using the Tensilon (Tensilon Universal Testing Machine "RTC-1210A" manufactured by Orientec Co., Ltd.), the bushing strength (MPa) of the obtained laminate was measured under the conditions of a crosshead speed of 10 mm/min.

[Method of evaluation of peelability]

The obtained laminate was placed in a dryer at 80 ° C and allowed to stand for 30 minutes. After the placement, the bushing strength (MPa) was measured in the same manner as in the above [Evaluation Method for Adhesion], and the peeling was evaluated by hand. In addition, if the hand can be easily peeled off, the peeling property is evaluated as "○"; if it cannot be peeled off by hand, the peeling property is evaluated as "x".

. "ARUFON (registered trademark) UP-1000": Acrylic plasticizer made by East Asia Synthetic Co., Ltd. (weight average molecular weight: 3,000, Tg: -77 °C)

. "W260": Ester-based plasticizer made by DIC Co., Ltd.

. "ADK CIZER (registered trademark) O-130P": epoxy crosslinking agent manufactured by ADEKA Co., Ltd.

It is known that the moisture-curing hot-melt urethane composition of the present invention can provide an adhesive having good adhesion and peelability.

On the other hand, Comparative Example 1 does not contain the form of the acrylic polymer (B), and has poor peelability and cannot be peeled off by hand.

Further, in Comparative Example 2, the ester-based plasticizer was used as the acrylic polymer (B), and the peeling property was poor, and it was impossible to peel off by hand.

In Comparative Example 3, the epoxy-based plasticizer was used as the acrylic polymer (B), and the compatibility with the urethane prepolymer (A) was poor, and a favorable laminate was not obtained.

Claims (5)

A moisture-curing hot-melt urethane composition characterized by comprising a urethane prepolymer (A) having an isocyanate group and an acrylic polymer (B). The moisture-curing hot-melt urethane composition according to claim 1, wherein the acrylic polymer (B) is contained in an amount of 100 parts by mass based on the urethane prepolymer (A) It is in the range of 1 to 100 parts by mass. The moisture-curing hot-melt urethane composition according to claim 1, wherein the acrylic polymer (B) has a weight average molecular weight of from 1,000 to 10,000. The moisture-curing hot-melt urethane composition according to claim 1, wherein the acrylic polymer (B) has a glass transition temperature of -10 ° C or lower. An adhesive comprising the moisture-curing hot-melt urethane composition according to any one of claims 1 to 4.