TW202003616A - Moisture-curable urethane hot melt resin composition and multilayer body - Google Patents

Abstract

The present invention provides: a moisture-curable polyurethane hot melt resin composition which is characterized by containing (i) a urethane prepolymer having an isocyanate group, which uses, as essential starting materials, (A) a polyol, (B) a polyisocyanate and (C) a compound that has one or more polymerizable unsaturated groups and two or more hydroxyl groups, (ii) a photopolymerization initiator and (iii) a light stabilizer; and a multilayer body which comprises a layer of a cured product of this moisture-curable polyurethane hot melt resin composition. The present invention also provides a multilayer body which is characterized by comprising a base material and a layer of a cured product of the above-described moisture-curable urethane hot melt resin composition. It is preferable that the light stabilizer (iii) contains a hindered amine compound (iii-X) and/or a nitrogen-containing heterocyclic compound (iii-Y).

Description

Moisture-curable urethane hot-melt resin composition and laminate

The present invention relates to a moisture-curable urethane hot-melt resin composition and a laminate.

Moisture-curable urethane hot-melt resin composition with urethane prepolymer as the main component is widely used in metal materials, wood materials, plastics, rubber, fiber products, synthetic leather, paper products, etc. Then, it is used in various fields such as building material paneling, decorative panels, automotive interior materials, and clothing.

The characteristics of the moisture-curable urethane hot-melt resin composition are: it is solvent-free like other hot-melt adhesives, and in addition to the initial adhesive strength obtained by cooling and solidification, In the next 24 to 72 hours, it reacts with the moisture in the air or the adherend to obtain the final adhesion strength and heat resistance that other hot-melt adhesives cannot show. However, it is not easy to further improve the initial adhesive strength by cooling and solidifying like other hot-melt adhesives.

As a method for solving this problem, there is disclosed a method of introducing a polymerizable unsaturated group at the end of a urethane prepolymer using 2-hydroxyethyl acrylate or the like (refer to, for example, Patent Document 1.). In this method, although sufficient initial adhesive strength can be obtained by ultraviolet curing, there is a problem that the final adhesive strength is poor.

In addition, in order to promote the use in various fields, the need for weather resistance of ultraviolet exposure has also increased, and the development of materials satisfying all of them is required.

[Prior Technical Literature] [Patent Literature]

Patent Literature 1 International Publication No. 2008/093653

The problem to be solved by the present invention is to provide a moisture-curable urethane hot-melt resin composition excellent in initial adhesive strength and final adhesive strength.

The invention provides a moisture-curable polyurethane hot-melt resin composition, which is characterized by containing a polyol (A), a polyisocyanate (B), and one or more polymerizable unsaturated groups, and , A compound (C) having two or more hydroxyl groups as an essential raw material, an isocyanate group-containing urethane prepolymer (i), and a photopolymerization initiator (ii); and a laminate having its hardened layer body.

The moisture-curable urethane hot-melt resin composition of the present invention is excellent in initial adhesion strength and final adhesion strength. In addition, when a light stabilizer is added, further weather resistance is also excellent.

[Forms for carrying out the invention]

The moisture-curable urethane hot-melt resin composition of the present invention contains a polyol (A), a polyisocyanate (B), and one or more polymerizable unsaturated groups, and more than two A hydroxy compound (C) is used as an essential raw material, a urethane prepolymer (i) having an isocyanate group, and a photopolymerization initiator (ii).

The aforementioned urethane prepolymer (i) is a compound (C) comprising a polyol (A), a polyisocyanate (B), and one or more polymerizable unsaturated groups and more than two hydroxyl groups ) Is obtained as a necessary raw material and has an isocyanate group.

As the above-mentioned polyol (A), for example, polyester polyol, polycaprolactone polyol, polyether polyol, polycarbonate polyol, acrylic polyol, polyurethane polyol, and the like can be used. These polyols can be used alone or in combination of two or more.

From the viewpoint of obtaining a more excellent mechanical strength of the film, the number average molecular weight of the polyol (A) is preferably in the range of 300 to 150,000, and more preferably in the range of 500 to 100,000. In addition, the number average molecular weight of the said polyol (A) shows the value measured by the gel permeation chromatography (GPC) method.

From the viewpoint of obtaining more excellent adhesive strength and the mechanical strength of the film, the amount of the polyol (A) used is preferably 50% in the moisture-curable urethane hot-melt resin composition. The range of ~95 mass% is more preferably 60~90 mass%.

As the polyisocyanate (B), for example, aliphatics such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethyl xylylene diisocyanate can be used. Polyisocyanate or alicyclic polyisocyanate; polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate isocyanate, xylene diisocyanate, benzene diisocyanate, toluene Aromatic polyisocyanates such as diisocyanate, naphthalene diisocyanate, etc.; these three polyisocyanates. These polyisocyanates may be used alone or in combination of two or more.

From the viewpoint of obtaining more excellent adhesive strength and the mechanical strength of the film, the amount of the polyisocyanate (B) used is preferably moisture curable urethane hot-melt resin composition 1 The range of ~50% by mass, more preferably the range of 3~40% by mass.

The aforementioned compound (C) has one or more polymerizable unsaturated groups and more than two hydroxyl groups. By using the compound (C) as a raw material for the urethane prepolymer (i), a polymerizable unsaturated group can be introduced into the molecule of the urethane prepolymer (i), and by Irradiation with ultraviolet rays or the like can provide excellent initial adhesion strength. In addition, since the urethane prepolymer (i) has an isocyanate group at the molecular terminal, it can be cured by moisture to obtain excellent final adhesion strength.

As the aforementioned compound (C), for example, a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and the following general compounds can be used The compound represented by the formula (4), the compound represented by the following general formula (5), the compound represented by the following general formula (6), and the like.

HO-R ¹ -OH (1)

(In the general formula (1), R ¹ represents a structure having at least one atomic group containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.)

HO-R ² O-R ³ -OR ⁴ -OH (2)

(In the general formula (2), R ² and R ⁴ are independent of each other and represent a structure having an atomic group containing a polymerizable unsaturated group in the ethylidene side chain, and R ³ represents an alkylene group having 1 to 5 carbon atoms. )

(In the general formula (3), R ⁵ and R ⁶ are each independently and represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 3.)

(In the general formula (4), R ⁷ represents a hydrogen atom or a methyl group, and n represents an integer of 2 to 3.)

(In the general formula (5), R ⁸ , R ⁹ , and R ¹⁰ each represent a hydrogen atom or a methyl group.)

(In the general formula (6), R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each represent a hydrogen atom or a methyl group.)

R ¹ in the aforementioned general formula (1) represents a structure having two or more atomic groups including a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms. For example, in neopentaerythritol di(meth)acrylate, R ¹ in the general formula (1) is a structure having two atomic groups containing a polymerizable unsaturated group on the side chain of a propylene group having 3 carbon atoms.

As specific examples of the compound represented by the aforementioned general formula (1), for example, neopentyl alcohol di(meth)acrylate [dimethylolpropane di(meth)acrylate], dimethylolmethane can be used Di(meth)acrylate (R ¹ in the general formula (1) has 3 carbon atoms and has 2 atomic groups having a polymerizable unsaturated group.), dihydroxyethylmethane di(meth)acrylic acid Ester, dihydroxyethylpropane di(meth)acrylate (R ¹ in the general formula (1) is 5 carbon atoms, and has two atomic groups having a polymerizable unsaturated group.), dipropanol methane Di(meth)acrylate, dipropanol propane di(meth)acrylate (R ¹ in the general formula (1) is a carbon atom having 7 atoms, and has 2 atomic groups having a polymerizable unsaturated group.) , Dibutanol methane di (meth) acrylate, dibutanol propane di (meth) acrylate (R ¹ in the general formula (1) is 9 carbon atoms, and has 2 with polymerizable unsaturated Radicals.) etc. These compounds may be used alone or in combination of two or more. From the viewpoint of obtaining more excellent initial adhesion strength, among these, it is preferable to use neopentaerythritol di(meth)acrylate and/or dimethylolmethane di(meth)acrylic acid ester.

In addition, in this invention, "(meth)acrylate" means either or both of acrylate and methacrylate.

R ² and R ⁴ in the general formula (2) have a structure having an atomic group containing a polymerizable unsaturated group in the ethylidene side chain. In the general formula (2), a structure having a total of 2 or more of the side chains of the ethylidene group having a polymerizable unsaturated group, preferably having a range of 2 or more and 5 or less, more preferably It has a range of 2 or more and 3 or less.

In addition, R ³ in the general formula (2) represents an alkylene group having 1 to 5 carbon atoms, and examples thereof include methylene group, ethyl group, propyl group, butyl group, and pentyl group.

As specific examples of the compound represented by the general formula (2), for example, bis(3-propenyloxy-2-hydroxypropoxy)methane (R ² and R ⁴ in the general formula (2) are Those with 2 carbon atoms and one atomic group with a polymerizable unsaturated group, R ³ is one with 1 carbon atom.), 1,2-bis(3-propenyloxy-2-hydroxypropoxy) Ethane (R ² and R ⁴ in the general formula (2) are ² carbon atoms and have an atomic group having a polymerizable unsaturated group, and R ³ is 2 carbon atoms.), 1,3- Bis(3-propenyloxy-2-hydroxypropoxy)propane (R ² and R ⁴ in the general formula (2) are those having ² carbon atoms and one atomic group having a polymerizable unsaturated group, R ³ is those with ³ carbon atoms.), 1,4-bis(3-propenyloxy-2-hydroxypropoxy)butane (R ² and R ⁴ in the general formula (2) are the number of carbon atoms 2 of which have an atomic group having a polymerizable unsaturated group, and R ³ is one having 4 carbon atoms.), 1,5-bis(3-propenyloxy-2-hydroxypropoxy)pentane ( In the general formula (2), R ² and R ⁴ are those having 2 carbon atoms and one atomic group having a polymerizable unsaturated group, and R ³ is those having 5 carbon atoms.) and the like. These compounds may be used alone or in combination of two or more. From the viewpoint of obtaining more excellent initial adhesion strength, among these, 1,4-bis(3-propenyloxy-2-hydroxypropoxy)butane is preferably used.

From the viewpoint of obtaining more excellent initial adhesion strength, the amount of the compound (C) used is preferably in the range of 0.01 to 50% by mass in the moisture-curable urethane hot-melt resin composition. It is more preferably in the range of 0.1 to 30% by mass, still more preferably in the range of 0.5 to 20% by mass, and particularly preferably in the range of 1 to 15% by mass.

The urethane prepolymer (i) is obtained by reacting the polyol (A) with the polyisocyanate (B) and the compound (C), and by using the hydroxyl group of the compound (C) Reacts with polyisocyanate (B), introduces polymerizable unsaturated groups into the molecule, and has moisture at the molecular end that can exist in the air or the substrate coated with the urethane prepolymer An isocyanate group forming a cross-linked structure.

As a method for producing the urethane prepolymer (i), for example, a polyisocyanate (B) may be added to the reaction vessel into which the polyol (A) and the compound (C) are added, and the The isocyanate group of the isocyanate (B) is produced by reacting under the conditions where the hydroxyl groups of the polyol (A) and the compound (C) become excessive.

From the viewpoint of obtaining more excellent initial adhesion strength and final adhesion strength, the isocyanate group and the polyol which the polyisocyanate (B) has when producing the urethane prepolymer (i) The equivalent ratio of hydroxyl groups (isocyanate group/hydroxyl group) possessed by (A) and compound (C) is preferably in the range of 1.1 to 10, more preferably in the range of 1.15 to 8.

From the viewpoint that more excellent final adhesion strength can be obtained, the isocyanate group content of the urethane prepolymer (i) (hereinafter abbreviated as "NCO%") is preferably 1 to 10. The mass% range is more preferably 1.5 to 8 mass% range. In addition, the NCO% of the said urethane prepolymer (i) shows the value measured by the potentiometric titration method based on JISK1603-1:2007.

The concentration of the polymerizable unsaturated group in the urethane prepolymer (i) is preferably in the range of 0.0004 to 2 mol/kg, and more preferably in the range of 0.001 to 1 mol/kg. In addition, the polymerizable unsaturated group concentration of the said urethane prepolymer (i) shows the numerical value calculated based on the reaction raw material used.

啉基-1-丙酮、2-苄基-2-二甲基 胺基-1-(4-

啉基苯基)-丁烷-1-酮等。該等之光聚合起始劑可單獨使用，亦可併用2種以上。 As the aforementioned photopolymerization initiator (ii), for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2 -Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, thioxanthone, thioxanthone derivatives, 2,2'-dimethoxy-1,2 -Diphenylethane-1-one, 2,4,6-trimethylbenzyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzyl) phenylphosphine oxide , 2-methyl-1-[4-(methylthio)phenyl]-2-

Plinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-

Phenylphenyl)-butane-1-one and the like. These photopolymerization initiators may be used alone or in combination of two or more.

From the viewpoint of obtaining more excellent ultraviolet curability, the amount of the photopolymerization initiator (ii) used is preferably polyol (A), polyisocyanate (B), compound (C), and light The total mass of the polymerization initiator (ii) and the light stabilizer (iii) is in the range of 0.0001 to 10% by mass, more preferably in the range of 0.005 to 5% by mass.

On the premise of obtaining more excellent weather resistance, the moisture-curable urethane hot-melt resin composition of the present invention preferably contains a light stabilizer (iii). Furthermore, the weather resistance in the present invention means especially the resistance to discoloration caused by the continuous irradiation of sunlight. The embodiments of the present invention indicate that the short-wavelength region equipped with the most faithful simulated sunlight is used at 295 to 365 nm. The result of the weather resistance test of the QUA accelerated weather resistance tester (manufactured by Q-LAB Corporation) of the UVA-340 lamp.

As the aforementioned light stabilizer (iii), for example, a hindered amine compound (iii-X), a nitrogen-containing heterocyclic compound (iii-Y), a thiol compound, a thioether compound, a benzophenone compound, benzophenone can be used Ester compounds, etc. These light stabilizers (iii) may be used alone or in combination of two or more. From the viewpoint of obtaining more excellent weather resistance, among these, it is preferable to use a hindered amine compound (iii-X) and/or a nitrogen-containing heterocyclic compound (iii-Y), and more preferably The hindered amine compound (iii-X) and the nitrogen-containing heterocyclic compound (iii-Y) are used in combination.

As the hindered amine compound (iii-X), for example, sebacic acid bis(2,2,6,6-tetramethyl-4-piperidyl), sebacic acid bis(1,2,2, 6,6-pentamethylpiperidin-4-yl), (2,2,6,6-tetramethyl-4-piperidinyl) 1,2,3,4-butane tetracarboxylate, (1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butane tetracarboxylate, (mixed 2,2,6,6-tetramethyl -4-piperidinyl/tridecyl) 1,2,3,4-butane tetracarboxylate, (mixed 1,2,2,6,6-pentamethyl-4-piperidinyl/tridecyl Group) 1,2,3,4-butane tetracarboxylate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triaza Spiro[4.5]decane-2,4-dione, etc. These compounds may be used alone or in combination of two or more.

}2-[4-[2-羥基-3-十二基氧基丙基]氧基]氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三

等三

化合物等。該等之三唑化合物可單獨使用，亦可併用2種以上。 As the aforementioned nitrogen-containing heterocyclic compound (iii-Y), for example, N,N-bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine, 2-[2-Hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2'-hydroxy-3',5'-di- Tertiary butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tertiarybutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2 -(2'-Hydroxy-3'-tertiary pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5' -Methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3',5'-di-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2 '-Hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole and other benzotriazole compounds or {mixed 2-[4-[2-hydroxy-3-dodecane Yloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tri

}2-[4-[2-Hydroxy-3-dodecyloxypropyl]oxy]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl )-1,3,5-three

Wait three

Compounds etc. These triazole compounds may be used alone or in combination of two or more.

From the viewpoint of obtaining more excellent weather resistance, the amount of the light stabilizer (iii) used is preferably 0.001 to 20 relative to 100 parts by mass of the urethane prepolymer (i). The range of parts by mass is more preferably 0.01 to 10 parts by mass, further more preferably 0.1 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass.

From the viewpoint of obtaining more excellent weather resistance, when the hindered amine compound (iii-X) and the nitrogen-containing heterocyclic compound (iii-Y) are used in combination, the mass ratio [(iii-X)/ (iii-Y)], preferably in the range of 90/10 to 10/90, more preferably in the range of 20/80 to 80/20, even more preferably in the range of 75/25 to 25/75.

From the viewpoint of obtaining more excellent weather resistance, the total mass of the hindered amine compound (iii-X) and the nitrogen-containing heterocyclic compound (iii-Y) is preferably the light stabilizer (iii) ) 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.

The moisture-curable urethane hot-melt resin composition of the present invention is further improved in order to use the urethane prepolymer (i) and the photopolymerization initiator (ii) as essential components The weather resistance preferably contains the aforementioned light stabilizer (iii), but may contain other additives as necessary.

As the aforementioned other additives, for example, hardening catalysts, adhesion-imparting agents, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent whitening agents, silane coupling agents, waxes, and thermoplastic resins can be used. These additives can be used alone or in combination of two or more.

Next, the laminate of the present invention will be described.

The laminate of the present invention has a substrate and a cured layer of the moisture-curable urethane hot-melt resin composition.

As the aforementioned substrate, for example, wood substrates such as plywood, MDF (medium density fiberboard), plastic plywood, etc.; metal substrates such as aluminum and iron; polyester, polyamide, polystyrene, and polycarbonate are used , Vinyl chloride, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyethylene, polypropylene and other resin-made sheet substrates; calcium silicate board; paper; metal foil; sheet; non-woven fabric, woven fabric and other fiber substrates ; Synthetic leather; paper; rubber substrate; glass substrate, etc. The thickness of the aforementioned substrate is determined according to the intended use, but it is, for example, in the range of 1 to 500 mm.

As a method of applying the moisture-curable urethane hot-melt resin composition on the substrate, for example, a moisture-curable urethane hot-melt resin that melts at 70 to 200°C may be mentioned. Composition, using roller coater, sprayer, T-die coater, knife coater, corner wheel coater and other coating methods; dispenser, spraying, inkjet printing, screen printing, lithography and other precision methods, etc. , Method of coating on substrate.

The cured layer of the moisture-curable urethane hot-melt composition is appropriately determined according to the application to be used, but it is, for example, in the range of 0.001 to 3 cm.

The moisture-curable urethane hot-melt composition applied as described above can obtain excellent initial adhesive strength by irradiating active energy rays. Examples of the active energy rays include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. From the viewpoint of easily obtaining the initial adhesion strength, among these, ultraviolet rays are preferred.

When irradiating the aforementioned ultraviolet rays, light sources such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, hydrogen lamps, deuterium lamps, halogen lamps, xenon lamps, carbon arc lamps, and fluorescent lamps can be used.

From the viewpoint of obtaining more excellent initial adhesion strength, the irradiation amount of the ultraviolet rays may be in the range of 0.05 to 5 J/cm ² , more preferably 0.1 to 3 J/cm ² , and particularly preferably 0.3 to 1.5 J /cm ² . In addition, the above-mentioned ultraviolet irradiation amount is based on the value measured using the UV tester "UVR-N1" by GS Yuasa International Ltd. in the wavelength range of 300-390 nm.

After the ultraviolet irradiation, in order to cure the isocyanate group of the urethane prepolymer (i), it is preferable to perform curing at a temperature of 20 to 40°C for 1 to 3 days.

The moisture-curable urethane hot-melt resin composition of the present invention described above is excellent in initial adhesion strength, final adhesion strength, and weather resistance.

[Example]

The present invention is explained in more detail below using examples.

[Synthesis Example 1] Synthesis of urethane prepolymer (i-1)

In a 2-liter 4-neck flask equipped with a stirrer and a thermometer, 4 parts by mass of dimethylol methane diacrylate and polyester polyol (reaction product of 1,6-hexanediol and adipic acid, number average molecular weight) : 4,500, hereinafter abbreviated as "PEs".) 76.6 parts by mass, and dehydrated under reduced pressure heating conditions until the total amount of water in the flask becomes 0.05% by mass.

Next, after cooling to 70°C, 1,4 parts by mass of 4,4′-diphenylmethane diisocyanate (hereinafter referred to as “MDI”) was added. After the temperature was raised to 100°C, a photopolymerization initiator (1-hydroxy ring) was added Hexyl phenyl ketone, hereinafter referred to as "Irg184".) 0.5 parts by mass, and reacted under nitrogen atmosphere at 110 ℃ for about 3 hours until the isocyanate group content becomes constant, thereby obtaining a urethane prepolymer (i- 1) (polymerizable unsaturated group concentration: 0.37 mol/kg, NCO%: 3.2%).

[Synthesis Example 2] Synthesis of urethane prepolymer (i-2)

In a 2-liter 4-neck flask equipped with a stirrer and a thermometer, feed 4 parts by mass of 1,4-bis(3-propenyloxy-2-hydroxypropoxy)butane and 79.9 parts by mass of PEs, and depressurize Under heating conditions, dehydration was performed until the total amount of water in the flask became 0.05% by mass.

Next, after cooling to 70°C, 15.6 parts by mass of MDI was added, after raising the temperature to 100°C, 0.5 parts by mass of Irg184 was added, and reacted at 110°C for about 3 hours under a nitrogen atmosphere until the content of isocyanate groups became constant, thereby obtaining amine groups Formate prepolymer (i-2) (polymerizable unsaturated group concentration: 0.23 mol/kg, NCO%: 2.6%).

[Synthesis Example 3] Synthesis of urethane prepolymer (i-3)

In a 2-liter 4-neck flask equipped with a stirrer and a thermometer, compound (3-1) (in the general formula (3), R ⁵ represents a hydrogen atom, R ⁶ represents a methyl group, and n represents an integer of 1) 4 mass Parts and 79.5 parts by mass of PEs, and under reduced pressure heating conditions, dehydration was performed until the total amount of water in the flask became 0.05% by mass.

Next, after cooling to 70°C, 16 parts by mass of MDI was added, and after raising the temperature to 100°C, 0.5 parts by mass of Irg184 was added and reacted at 110°C for about 3 hours under a nitrogen atmosphere until the content of isocyanate groups became constant, thereby obtaining amine groups Formate prepolymer (i-3) (polymerizable unsaturated group concentration: 0.24 mol/kg, NCO%: 2.7%).

[Synthesis Example 4] Synthesis of urethane prepolymer (i-4)

In a 2-liter 4-neck flask equipped with a stirrer and a thermometer, the compound (3-2) was fed (In the general formula (3), R ⁵ represents a methyl group, R ⁶ represents a hydrogen atom, and n represents an integer of 1.) 4 mass Parts and 79.9 parts by mass of PEs, and under reduced pressure heating conditions, dehydration is performed until the total amount of water in the flask becomes 0.05% by mass.

Next, after cooling to 70°C, 15.6 parts by mass of MDI was added, after raising the temperature to 100°C, 0.5 parts by mass of Irg184 was added, and reacted at 110°C for about 3 hours under a nitrogen atmosphere until the content of isocyanate groups became constant, thereby obtaining amine groups Formate prepolymer (i-4) (polymerizable unsaturated group concentration: 0.23 mol/kg, NCO%: 2.5%).

[Synthesis Example 5] Synthesis of urethane prepolymer (i-5)

In a 2-liter 4-neck flask equipped with a stirrer and a thermometer, compound (4-1) (in the general formula (4), R ⁷ represents a hydrogen atom and n represents an integer of 3) 4 parts by mass and 79.9 parts by mass of PEs Parts, and under reduced pressure heating conditions, dehydration was performed until the total amount of water in the flask became 0.05% by mass.

Next, after cooling to 70°C, 15.6 parts by mass of MDI was added, after raising the temperature to 100°C, 0.5 parts by mass of Irg184 was added, and reacted at 110°C for about 3 hours under a nitrogen atmosphere until the content of isocyanate groups became constant, thereby obtaining amine groups Formate prepolymer (i-5) (polymerizable unsaturated group concentration: 0.23 mol/kg, NCO%: 2.6%).

[Synthesis Example 6] Synthesis of urethane prepolymer (i-6)

In a 2-liter 4-neck flask equipped with a stirrer and a thermometer, compound (5-1) (in the general formula (5), R ⁸ represents a hydrogen atom, R ⁹ and R ¹⁰ represent a methyl group.) 4 parts by mass, and 81.5 parts by mass of PEs were dehydrated under reduced pressure heating conditions until the total amount of water in the flask became 0.05% by mass.

Next, after cooling to 70°C, 14 parts by mass of MDI was added, after raising the temperature to 100°C, 0.5 parts by mass of Irg184 was added, and reacted at 110°C for about 3 hours under a nitrogen atmosphere until the content of isocyanate groups became constant, thereby obtaining amine groups Formate prepolymer (i-6) (polymerizable unsaturated group concentration: 0.16 mol/kg, NCO%: 2.2%).

[Synthesis Example 7] Synthesis of urethane prepolymer (i-7)

In a 2-liter 4-neck flask equipped with a stirrer and a thermometer, compound (6-1) (in the general formula (6), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ all represent methyl groups.) 4 parts by mass, And 82.5 parts by mass of PEs, and under reduced pressure heating conditions, dehydration until the total amount of water in the flask becomes 0.05% by mass.

Next, after cooling to 70°C, 13 parts by mass of MDI was added, after raising the temperature to 100°C, 0.5 parts by mass of Irg184 was added, and reacted at 110°C for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, thereby obtaining amine groups Formate prepolymer (i-7) (polymerizable unsaturated group concentration: 0.13 mol/kg, NCO%: 2.1%).

[Comparative Synthesis Example 1] Synthesis of urethane prepolymer (iR-1)

In a 2-liter 4-neck flask equipped with a stirrer and a thermometer, 89.5 parts by mass of PEs were fed, and dehydration was carried out under reduced pressure heating conditions until the total amount of water in the flask became 0.05% by mass.

Next, after cooling to 70°C, 10.5 parts by mass of MDI was added, and after raising the temperature to 100°C, the reaction was carried out at 110°C for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, thereby obtaining a urethane prepolymer ( iR-1) (polymerizable unsaturated group concentration: 0 mol/kg, NCO%: 1.7%).

[Comparative Synthesis Example 2] Synthesis of urethane prepolymer (iR-2)

In a 2-liter 4-neck flask equipped with a stirrer and a thermometer, 87.2 parts by mass of PEs were fed and dehydrated under reduced pressure heating conditions until it became 0.05% by mass relative to the total amount of water in the flask.

Next, after cooling to 70°C, 10.3 parts by mass of MDI was added, after raising the temperature to 100°C, 0.5 parts by mass of Irg184 was added, and reacted at 110°C for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, and acrylic acid 2 was added -Hydroxyethyl ester (hereinafter abbreviated as "HEA") 2 parts by mass, the reaction is carried out for about 1 hour, thereby obtaining a urethane prepolymer (iR-2) (polymerizable unsaturated group concentration: 0.17mol/kg , NCO%: 1.0%).

[Example 1]

By blending 100 parts by mass of the urethane prepolymer (i-1) obtained in Synthesis Example 1, and 0.5 parts by mass of a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), a moisture hardening type was obtained Polyurethane hot-melt resin composition.

[Example 2]

Blended with 100 parts by mass of the urethane prepolymer (i-1) obtained in Synthesis Example 1, 0.5 parts by mass of a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), and bis(1 sebacate) ,2,2,6,6-pentamethylpiperidin-4-yl) (hereinafter referred to as "hindered amine (1)".) 1 part by mass, and 2-[2-hydroxy-3,5-bis( α,α-dimethylbenzyl)phenyl]-2H-benzotriazole (hereinafter abbreviated as "benzotriazole (1)".) 1 part by mass to obtain moisture-curable polyurethane Hot melt resin composition.

[Example 3]

化合物(BASF公司製「Tinuvin(註冊商標)400」，以下簡稱為「三

(1)」。)1質量份，得到濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。 100 parts by mass of the carbamate prepolymer (i-2) obtained in Synthesis Example 2, 0.5 parts by mass of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), and hindered amine (1) 1 Quality parts, and three

Compound ("Tinuvin (registered trademark) 400" manufactured by BASF, hereinafter referred to as "Three

(1)". ) 1 part by mass to obtain a moisture-curable polyurethane hot-melt resin composition.

[Example 4]

100 parts by mass of the carbamate prepolymer (i-3) obtained in Synthesis Example 3, 0.5 parts by mass of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), and hindered amine (2) 1 1 part by mass and benzotriazole (1) 1 part by mass to obtain a moisture-curable polyurethane hot-melt resin composition.

[Example 5]

(1)1質量份，得到濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。 100 parts by mass of the carbamate prepolymer (i-4) obtained in Synthesis Example 4, 0.5 parts by mass of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), and hindered amine (2) 1 Quality parts, and three

(1) 1 part by mass to obtain a moisture-curable polyurethane hot-melt resin composition.

[Example 6]

Blended with 100 parts by mass of the carbamate prepolymer (i-5) obtained in Synthesis Example 5, 0.5 parts by mass of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), and hindered amine (1) 1.5 The mass part and 1.5 mass parts of benzotriazole (1) obtained the moisture hardening type polyurethane hot-melt resin composition.

[Example 7]

100 parts by mass of the carbamate prepolymer (i-6) obtained in Synthesis Example 6, 0.5 parts by mass of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), and hindered amine (1) 1 The mass part and 1.5 mass parts of benzotriazole (1) obtained the moisture hardening type polyurethane hot-melt resin composition.

[Example 8]

100 parts by mass of the carbamate prepolymer (i-7) obtained in Synthesis Example 7, 0.5 parts by mass of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), and hindered amine (1) 1.5 1 part by mass and benzotriazole (1) 1 part by mass to obtain a moisture-curable polyurethane hot-melt resin composition.

[Comparative Example 1]

100 parts by mass of the urethane prepolymer (iR-1) obtained in Comparative Synthesis Example 1, 1 part by mass of the hindered amine (1), and 1 part by mass of the benzotriazole (1) were obtained. Hardened polyurethane hot-melt resin composition.

[Comparative Example 2]

100 parts by mass of the urethane prepolymer (iR-2) obtained in Comparative Synthesis Example 2, 0.5 parts by mass of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), and hindered amine (1) 1 part by mass and 1 part by mass of benzotriazole (1) gave a moisture-curable polyurethane hot-melt resin composition.

[Measurement method of number average molecular weight]

The number average molecular weights of polyols and the like used in Synthesis Examples and Comparative Synthesis Examples represent values measured by gel permeation chromatography (GPC) method under the following conditions.

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

Tubing: The following tubing made by Tosoh Corporation was used in series.

"TSKgel G5000" (7.8mmI.D.×30cm)×1

"TSKgel G4000" (7.8mmI.D.×30cm)×1

"TSKgel G3000" (7.8mmI.D.×30cm)×1

"TSKgel G2000" (7.8mmI.D.×30cm)×1

Detector: RI (Differential Refractometer)

Column temperature: 40℃

Eluent: Tetrahydrofuran (THF)

Flow rate: 1.0mL/min

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

Standard sample: Use the following standard polystyrene to make a calibration line.

(Standard polystyrene)

"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[Evaluation method of initial bonding strength] (1) Test method for initial peelability

After the moisture-curable urethane hot-melt resin compositions obtained in Examples and Comparative Examples were each melted at 120°C for 1 hour, a polyethylene terephthalate group with a thickness of 200 μm corona-treated On the material, a roll coater was used to apply a thickness of 100 μm. Then, using a high-pressure mercury lamp on the coated surface, irradiated with 0.65 J/cm ² of ultraviolet rays, and a polyethylene terephthalate substrate having a thickness of 200 μm corona treatment was further laminated on the irradiated surface, and After 3 minutes, the 180° peel strength (N/inch) was measured according to JISK7311-1995, and evaluated as follows.

"T": 60N/inch or more

"F": less than 60N/inch

(2) Test method for initial heat creep resistance

After each of the moisture-curable urethane hot-melt resin compositions obtained in Examples and Comparative Examples was melted at 120° C. for 1 hour, on a polyethylene terephthalate substrate, a roll coater was used to The coating is applied to a thickness of 50 μm. After that, a high-pressure mercury lamp was used on the coated surface, and ultraviolet rays of 0.65 J/cm ² were irradiated, and MDF (medium density fiberboard) was placed on the irradiated surface and bonded. After 5 minutes after bonding, under a 35°C environment, apply a load of 75g to the 90mm direction for a width of 25mm, and measure the peeling length of the polyethylene terephthalate substrate after 15 minutes, as follows Make an evaluation.

"T": less than 5mm

"F": 5mm or more

[Evaluation method of final strength]

After each of the moisture-curable urethane hot-melt resin compositions obtained in Examples and Comparative Examples was melted at 120° C. for 1 hour, on a polyethylene terephthalate substrate, a roll coater was used to The coating is applied to a thickness of 50 μm. After that, a high-pressure mercury lamp was used on the coated surface, and ultraviolet rays of 0.65 J/cm ² were irradiated, and MDF (medium density fiberboard) was placed on the irradiated surface, and bonded. After curing the test piece for 72 hours in an environment of 23°C and a humidity of 50%, a load of 500g is applied to the 90mm direction at an environment of 80°C for a width of 25 mm, and the measurement is made after 15 minutes have passed after 1 hour The peeling length of the polyethylene terephthalate substrate was evaluated as follows.

"T": less than 5mm

"F": 5mm or more

[Evaluation method of weather resistance]

After the moisture-curable urethane hot-melt resin compositions obtained in Examples and Comparative Examples were each melted at 120°C for 1 hour, they were placed on release paper placed on a hot plate previously heated to 120°C. The coating is applied so as to have a thickness of 100 μm. A film was obtained by storing the coated product at 25°C and 50% humidity for 24 hours and curing. Using this film, a UVA weather resistance tester "QUV/basic" equipped with a UVA-340 electric ball (UV exposure: 0.78W/m ² and a temperature of 45°C) was used to perform the UV irradiation test according to the color change before and after UV irradiation The difference (ΔE) was evaluated as follows for weather resistance.

"1": △E is 1 or less.

"2": △E exceeds 1 and is 5 or less.

"3": △E exceeds 5 and is 7.5 or less.

"4": △E exceeds 7.5.

The moisture-curable urethane hot-melt resin composition of the present invention is known to have excellent initial adhesive strength and final adhesive strength. If the light stabilizer is further blended, it is known that it has excellent weather resistance.

On the other hand, in Comparative Example 1, the compound (C) was not used, and a polymerizable unsaturated group was not introduced into the urethane prepolymer (i), but the initial adhesion strength was poor.

Comparative Example 2 is a case where 2-hydroxyethyl acrylate is used instead of the compound (C) as a raw material, but the final adhesion strength is poor.

Claims (8)

A moisture-curable polyurethane hot-melt resin composition, which is characterized by containing polyol (A), polyisocyanate (B), and having at least one polymerizable unsaturated group, and having 2 A urethane prepolymer (i) having an isocyanate group and a photopolymerization initiator (ii) having at least one hydroxy compound (C) as essential raw materials. The moisture-curable polyurethane hot-melt resin composition according to claim 1, wherein the compound (C) is selected from the group consisting of compounds represented by the following general formula (1) and the following general formula (2 ), the compound represented by the following general formula (3), the compound represented by the following general formula (4), the compound represented by the following general formula (5), and the following general formula (6) One or more of the group of compounds shown; HO-R ¹ -OH (1) (In the general formula (1), R ¹ represents that the side chain of a linear alkylene group having 1 to 9 carbon atoms has 1 The structure of more than one atom group containing polymerizable unsaturated groups); HO-R ² OR ³ -OR ⁴ -OH (2) (In the general formula (2), R ² and R ⁴ are each independent and represent the ethyl group The side chain of has a structure of an atomic group containing a polymerizable unsaturated group, R ³ represents an alkylene group having 1 to 5 carbon atoms);

(In the general formula (3), R ⁵ and R ⁶ are each independent and represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 3);

(In the general formula (4), R ⁷ represents a hydrogen atom or a methyl group, and n represents an integer of 2 to 3);

(In the general formula (5), R ⁸ , R ⁹ , and R ¹⁰ each represent a hydrogen atom or a methyl group);

(In the general formula (6), R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each represent a hydrogen atom or a methyl group). The moisture-curable polyurethane hot-melt resin composition according to claim 1 or 2, wherein the concentration of the polymerizable unsaturated group of the urethane prepolymer (i) is 0.0004 to 2 mol/kg range. The moisture-curable polyurethane hot-melt resin composition according to any one of claims 1 to 3, wherein the isocyanate group content of the urethane prepolymer (i) is 1 to 10 mass % Range. The moisture-curable polyurethane hot-melt resin composition according to any one of claims 1 to 4, which further contains a light stabilizer (iii). The moisture-curable polyurethane hot-melt resin composition according to claim 5, wherein the light stabilizer (iii) contains a hindered amine compound (iii-X), and/or a nitrogen-containing heterocyclic compound (iii) -Y). The moisture-curable polyurethane hot-melt resin composition according to claim 5 or 6, wherein the content of the light stabilizer (iii) is relative to 100 masses of the polyurethane prepolymer (i) The part is in the range of 0.001 to 20 parts by mass. A laminated body characterized by having a substrate and a cured layer of a moisture-curable urethane hot-melt resin composition according to any one of claims 1 to 7.