Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated

Definitions

• the present invention relates to a moisture curable urethane hot melt resin composition and a laminate.
• Moisture curable urethane hot melt resin composition mainly composed of urethane prepolymer is widely used for bonding metal materials, wood materials, plastics, rubber, textile products, synthetic leather, paper products, etc. It is used in various fields such as decorative panels, automobile interior materials, and clothing.
• the moisture-curable urethane hot-melt resin composition is characterized by being solvent-free as with other hot-melt adhesives, and in addition to obtaining initial adhesive strength by cooling and solidification, and further, about 24 to 72 hours after adhesion. By reacting in the air or with the moisture of the adherend within this time, it is possible to obtain the final adhesive strength and heat resistance that cannot be expressed by other hot melt adhesives. However, as with other hot melt adhesives, it is not easy to further increase the initial adhesive strength only by cooling and solidifying.
• the problem to be solved by the present invention is to provide a moisture-curable urethane hot melt resin composition having excellent initial adhesive strength, final adhesive strength, and weather resistance.
• the present invention provides an isocyanate group comprising, as essential raw materials, a polyol (A), a polyisocyanate (B), and a compound (C) having at least one polymerizable unsaturated group and having at least two hydroxyl groups.
• a moisture curable polyurethane hot melt resin composition characterized by containing a urethane prepolymer (i), a photopolymerization initiator (ii), and a light stabilizer (iii), and a cured product layer thereof, The laminated body which has is provided.
• the moisture curable urethane hot melt resin composition of the present invention is excellent in initial adhesive strength, final adhesive strength, and weather resistance.
• the moisture curable urethane hot melt resin composition of the present invention comprises a polyol (A), a polyisocyanate (B), a compound having one or more polymerizable unsaturated groups and two or more hydroxyl groups (C ) And a urethane prepolymer having an isocyanate group (i) a photopolymerization initiator (ii) and a light stabilizer (iii).
• the urethane prepolymer (i) is an essential raw material comprising a polyol (A), a polyisocyanate (B), and a compound (C) having one or more polymerizable unsaturated groups and two or more hydroxyl groups. Obtained and having an isocyanate group.
• polyester polyol for example, polyester polyol, polycaprolactone polyol, polyether polyol, polycarbonate polyol, acrylic polyol, polyurethane polyol and the like can be used. These polyols may be used alone or in combination of two or more.
• the number average molecular weight of the polyol (A) is preferably in the range of 300 to 150,000, more preferably in the range of 500 to 100,000, from the viewpoint that a more excellent mechanical strength of the film can be obtained.
• the number average molecular weight of the said polyol (A) shows the value measured by the gel permeation chromatography (GPC) method.
• polyol (A) As for the amount of the polyol (A) used, polyol (A), polyisocyanate (B), compound (C) and photopolymerization are started from the point that even better adhesive strength and mechanical strength of the film can be obtained.
• the total mass of the agent (ii) and the light stabilizer (iii) is preferably in the range of 50 to 95% by mass, and more preferably in the range of 60 to 90% by mass.
• polyisocyanate (B) examples include aliphatic polyisocyanates or cycloaliphatic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate; polymethylene polyphenyl polyisocyanate, Aromatic polyisocyanates such as diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, xylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate; these isocyanurate bodies and the like can be used. These polyisocyanates may be used alone or in combination of two or more.
• the amount of the polyisocyanate (B) used is obtained from the viewpoint that a further excellent adhesive strength and mechanical strength of the film can be obtained. It is preferably in the range of 1 to 50% by weight, more preferably in the range of 3 to 40% by weight, based on the total weight of the initiator (ii) and the light stabilizer (iii).
• the compound (C) has one or more polymerizable unsaturated groups and two or more hydroxyl groups.
• a polymerizable unsaturated group can be introduced into the molecule of the urethane prepolymer (i). Adhesive strength can be obtained. Furthermore, since the urethane prepolymer (i) has an isocyanate group at the molecular end, excellent final adhesive strength can be obtained by moisture curing.
• Examples of the compound (C) include 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 formula (4).
• the compound shown, the compound shown by the following general formula (5), the compound shown by the following general formula (6), etc. can be used.
• 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.
• R 2 and R 4 each independently represent a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group, and R 3 has 1 to 5 carbon atoms. Represents an alkylene group of
• R 5 and R 6 each independently represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 3.
• R 7 represents a hydrogen atom or a methyl group, and n represents an integer of 2 to 3)
• R 8 , R 9 and R 10 each represent a hydrogen atom or a methyl group.
• R 11 , R 12 , R 13 , and R 14 each represent a hydrogen atom or a methyl group.
• R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.
• pentaerythritol di (meth) acrylate has a structure in which R 1 in the general formula (1) has two atomic groups containing a polymerizable unsaturated group in the side chain of a propylene group having 3 carbon atoms.
• the compound represented by the general formula (1) include, for example, pentaerythritol di (meth) acrylate [dimethylolpropane di (meth) acrylate], dimethylolmethane di (meth) acrylate (general formula (1) R 1 in them has 3 carbon atoms and has 2 atomic groups having a polymerizable unsaturated group.), Diethylolmethane di (meth) acrylate, diethylolpropane di (meth) acrylate (R 1 in the general formula (1) has 5 carbon atoms and has 2 atomic groups having a polymerizable unsaturated group), dipropanolmethane di (meth) acrylate, dipropanol propanedioic R 1 in (meth) acrylate (formula (1) is of a carbon atoms 7, der having two atomic group having a polymerizable unsaturated group .), Di-butanol methane di R 1 in (meth)
• These compounds may be used alone or in combination of two or more.
• pentaerythritol di (meth) acrylate and / or dimethylolmethane di (meth) acrylate from the viewpoint that a further excellent initial adhesive strength can be obtained.
• (meth) acrylate refers to either one 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 side chain of the ethylene group.
• it has a total of two or more structures having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group, preferably in the range of 2 or more and 5 or less, More preferably, it has in the range of 2 or more and 3 or less.
• R 3 in the general formula (2) represents an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentyl group.
• Specific examples of the compound represented by the general formula (2) include, for example, bis (3-acryloyloxy-2-hydroxypropoxy) methane (R 2 and R 4 in the general formula (2) are those having 2 carbon atoms. 1 having an atomic group having a polymerizable unsaturated group, and R 3 is one having 1 carbon atom.), 1,2-bis (3-acryloyloxy-2-hydroxypropoxy) ethane ( R 2 and R 4 in the general formula (2) are those having 2 carbon atoms, having one atomic group having a polymerizable unsaturated group, and R 3 is having 2 carbon atoms.
• 1,3-bis (3-acryloyloxy-2-hydroxypropoxy) propane (wherein R 2 and R 4 in the general formula (2) have 2 carbon atoms and have an atomic group having a polymerizable unsaturated group) are those having one 1, R 3 is a carbon atom 3 is of.), 1,4-bis R 2 and R 4 in (3-acryloyloxy-2-hydroxypropoxy) butane (formula (2) by way of 2 carbon atoms, a polymerizable unsaturated And R 3 has 4 carbon atoms.), 1,5-bis (3-acryloyloxy-2-hydroxypropoxy) pentane (in general formula (2)) And R 2 and R 4 have 2 carbon atoms, have one atomic group having a polymerizable unsaturated group, and R 3 has 5 carbon atoms). it can.
• These compounds may be used alone or in combination of two or more. Among these, it is preferable to use 1,4-bis (3-acryloyloxy-2-hydroxypropoxy) butane from the viewpoint that a
• the total mass of the agent (iii) is preferably in the range of 0.01 to 50% by mass, 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. A range of ⁇ 15% by weight is particularly preferred.
• the urethane prepolymer (i) is obtained by reacting the polyol (A), the polyisocyanate (B) and the compound (C), and the hydroxyl group of the compound (C) is polyisocyanate (B). ) To form a cross-linked structure by reacting with moisture present in the air or in the substrate to which the urethane prepolymer is applied. It has an isocyanate group at the molecular end.
• the polyisocyanate (B) is put into a reaction vessel containing the polyol (A) and the compound (C), and the isocyanate group contained in the polyisocyanate (B).
• it can manufacture by making it react on the conditions which become excess with respect to the hydroxyl group which the said polyol (A) and compound (C) have.
• isocyanate group / hydroxyl group As an equivalent ratio (isocyanate group / hydroxyl group) between the isocyanate group possessed by the polyisocyanate (B) and the hydroxyl group possessed by the polyol (A) and the compound (C) when the urethane prepolymer (i) is produced. From the standpoint of obtaining even better initial and final adhesive strengths, it is preferably in the range of 1.1 to 10, and more preferably in the range of 1.15 to 8.
• the isocyanate group content (hereinafter abbreviated as “NCO%”) of the urethane prepolymer (i) is in the range of 1 to 10% by mass from the standpoint of obtaining even better final adhesive strength. The range of 1.5 to 8% by mass is more preferable.
• the NCO% of the urethane prepolymer (i) is a value measured by potentiometric titration in accordance with JISK1603-1: 2007.
• the polymerizable unsaturated group concentration of 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.
• concentration of the said urethane prepolymer (i) shows the value computed based on the used reaction raw material.
• Examples of the photopolymerization initiator (ii) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl].
• a photoinitiator (ii) As the usage-amount of the said photoinitiator (ii), a polyol (A), a polyisocyanate (B), a compound (C), and a photoinitiator (ii) from the point which can obtain the further outstanding ultraviolet-curing property. Is preferably in the range of 0.0001 to 10% by mass, and more preferably in the range of 0.005 to 5% by mass in the total mass of the light stabilizer (iii).
• the light stabilizer (iii) is an essential component for obtaining excellent weather resistance.
• the weather resistance of the present invention means discoloration resistance due to continuous irradiation of sunlight, and in the embodiment of the present invention, UVA that most faithfully simulates a short wavelength region of 295 to 365 nm of sunlight.
• the results of a weather resistance test using a QUV accelerated weather resistance tester (Q-LAB Corporation) equipped with a -340 lamp are shown.
• Examples of the light stabilizer (iii) include hindered amine compounds (iii-X), nitrogen-containing heterocyclic compounds (iii-Y), thiol compounds, thioether compounds, benzophenone compounds, and benzoate compounds. These light stabilizers (iii) may be used alone or in combination of two or more. Among these, it is preferable to use the hindered amine compound (iii-X) and / or the nitrogen-containing heterocyclic compound (iii-Y) from the viewpoint that a further excellent weather resistance can be obtained, and the hindered amine compound (iii- More preferably, X) and the nitrogen-containing heterocyclic compound (iii-Y) are used in combination.
• hindered amine compound (iii-X) examples include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethylpiperidine sebacate).
• -4-yl tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl- 4-piperidyl) 1,2,3,4-butanetetracarboxylate, (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) 1,2,3,4-butanetetracarboxylate, Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) 1,2,3,4-butanetetracarboxylate, 8-acetyl-3-dodecyl-7,7 9,9-tetramethyl-1,3,8-triazas
• nitrogen-containing heterocyclic compound (iii-Y) examples include N, N-bis (2-ethylhexyl)-[(1,2,4-triazol-1-yl) methyl] amine, 2- [2 -Hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-amyl-5′-isobutylphenyl) ) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-isobutyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydride) Roxy-3'-is
• the amount of the light stabilizer (iii) used is in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the urethane prepolymer (i) from the viewpoint of obtaining even better weather resistance.
• the range of 0.01 to 10 parts by mass is more preferable, the range of 0.1 to 5 parts by mass is still more preferable, and the range of 0.5 to 3 parts by mass is particularly preferable.
• the mass ratio [(iii-X) / (Iii-Y)] is preferably in the range of 90/10 to 10/90, more preferably in the range of 20/80 to 80/20, and still more preferably in the range of 75/25 to 25/75.
• the total mass of the hindered amine compound (iii-X) and the nitrogen-containing heterocyclic compound (iii-Y) is 70 mass in the light stabilizer (iii) from the viewpoint that much more excellent weather resistance is obtained. % Or more, preferably 80% by mass or more, and more preferably 90% by mass or more.
• the moisture curable urethane hot melt resin composition of the present invention contains the urethane prepolymer (i), the photopolymerization initiator (ii), and the light stabilizer (iii) as essential components. Depending on the case, other additives may be contained.
• additives examples include a curing catalyst, a tackifier, a plasticizer, a stabilizer, a filler, a dye, a pigment, a fluorescent brightening agent, a silane coupling agent, a wax, and a thermoplastic resin. It can. These additives may be used alone or in combination of two or more.
• the laminate of the present invention has a base material and a cured product layer of the moisture curable urethane hot melt resin composition.
• the base material examples include wood base materials such as plywood, MDF (medium density fiber board), and particle board; metal base materials such as aluminum and iron; polyester, polyamide, polystyrene, polycarbonate, vinyl chloride, and ethylene-vinyl acetate.
• Sheet base material obtained using resin such as polymer, polyvinyl alcohol, polyethylene, polypropylene; calcium silicate plate; paper; metal foil; veneer; fiber base material such as nonwoven fabric and woven fabric; synthetic leather; paper; rubber Substrate; glass substrate and the like can be used.
• the thickness of the base material is determined according to the application used, and is, for example, in the range of 1 to 500 mm.
• Examples of the method for applying the moisture curable urethane hot melt resin composition on the substrate include, for example, a moisture curable urethane hot melt resin composition melted at 70 to 200 ° C., a roll coater, a spray coater, T -Coating methods such as a tie coater, knife coater, comma coater; and a method of applying to a substrate using a precision method such as dispenser, spray, inkjet printing, screen printing, offset printing, etc.
• the cured product layer of the moisture curable urethane hot melt composition is appropriately determined according to the intended use, and is, for example, in the range of 0.001 to 3 cm.
• the applied moisture curable urethane hot melt composition can obtain excellent initial adhesive strength by irradiating with active energy rays.
• active energy rays include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. Among these, ultraviolet rays are preferable because initial adhesive strength can be easily obtained.
• a light source such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a hydrogen lamp, a deuterium lamp, a halogen lamp, a xenon lamp, a carbon arc lamp, or a fluorescent lamp can be used.
• the irradiation amount of the ultraviolet rays is from 0.05 to 5 J / cm 2 , more preferably from 0.1 to 3 J / cm 2 , and particularly preferably from 0.3 to 1 from the viewpoint that a further excellent initial adhesive strength is obtained. It may be in the range of 5 J / cm 2 .
• the amount of UV irradiation is based on a value measured in a wavelength range of 300 to 390 nm using a UV checker “UVR-N1” manufactured by GS Yuasa Corporation.
• the isocyanate group of the urethane prepolymer (i) after the ultraviolet irradiation it is preferably cured 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 is excellent in initial adhesive strength, final adhesive strength, and weather resistance.
• MDI 4,4′-diphenylmethane diisocyanate
• urethane prepolymer (i-3) polymerizable unsaturated group concentration; 0.24 mol / kg, NCO%; 2.7%) was obtained.
• urethane prepolymer (i-4) polymerizable unsaturated group concentration; 0.23 mol / kg, NCO%; 2.5%) was obtained.
• urethane prepolymer (i-6) polymerizable unsaturated group concentration; 0.16 mol / kg, NCO%; 2.2%) was obtained.
• urethane prepolymer (i-7) (polymerizable unsaturated group concentration; 0.13 mol / kg, NCO%; 2.1%) was obtained.
• HSA 2-hydroxyethyl acrylate
• Example 1 100 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), bis (1,2,2,6,6) sebacate -Pentamethylpiperidin-4-yl) (hereinafter abbreviated as "hindered amine (1)”) 1 part by mass, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl]- One part by weight of 2H-benzotriazole (hereinafter abbreviated as “benzotriazole (1)”) was blended to obtain a moisture curable polyurethane hot melt resin composition.
• a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone
• bis (1,2,2,6,6) sebacate -Pentamethylpiperidin-4-yl) hereinafter abbreviated as "hindered amine (1)”
• Example 2 100 parts by mass of urethane prepolymer (i-2) obtained in Synthesis Example 2, 0.5 part by mass of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), 1 part by mass of hindered amine (1), triazine compound (BASF Corporation) “Tinuvin (registered trademark) 400” (hereinafter abbreviated as “triazine (1)”) 1 part by mass was blended to obtain a moisture-curable polyurethane hot melt resin composition.
• photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone
• hindered amine (1) triazine compound (BASF Corporation) “Tinuvin (registered trademark) 400”
• Example 3 100 parts by mass of the urethane prepolymer (i-3) obtained in Synthesis Example 3, 0.5 parts by mass of a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), 1 part by mass of a hindered amine (2), and benzotriazole (1) 1 part by mass was blended to obtain a moisture curable polyurethane hot melt resin composition.
• Example 4 100 parts by mass of urethane prepolymer (i-4) obtained in Synthesis Example 4, 0.5 part by mass of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), 1 part by mass of hindered amine (2), triazine (1) 1 By blending parts by mass, a moisture-curable polyurethane hot melt resin composition was obtained.
• Example 5 100 parts by mass of the urethane prepolymer (i-5) obtained in Synthesis Example 5, 0.5 parts by mass of a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), 1.5 parts by mass of hindered amine (1), benzotriazole ( 1) 1.5 parts by mass was blended to obtain a moisture curable polyurethane hot melt resin composition.
• Example 6 100 parts by mass of urethane prepolymer (i-6) obtained in Synthesis Example 6, 0.5 part by mass of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), 1 part by mass of hindered amine (1), benzotriazole (1) 1.5 parts by mass was blended to obtain a moisture curable polyurethane hot melt resin composition.
• Example 7 100 parts by mass of the urethane prepolymer (i-7) obtained in Synthesis Example 7, 0.5 parts by mass of a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), 1.5 parts by mass of hindered amine (1), benzotriazole ( 1) 1 part by mass was blended to obtain a moisture curable polyurethane hot melt resin composition.
• 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 peel length of the terephthalate substrate was measured and evaluated as follows. “T”: less than 5 mm “F”: 5 mm or more
• the weather resistance was evaluated as follows by the difference in color change ( ⁇ E) before and after UV irradiation. “1”; ⁇ E is 1 or less. “2”; ⁇ E exceeds 1 and is 5 or less. “3”; ⁇ E is more than 5 and 7.5 or less. “4”; ⁇ E exceeds 7.5.
• the moisture curable urethane hot melt resin composition of the present invention was found to have excellent initial adhesive strength, final adhesive strength, and weather resistance.
• Comparative Example 1 was an embodiment in which the compound (C) was not used and no polymerizable unsaturated group was introduced into the urethane prepolymer (i), but the initial adhesive strength was poor.
• Comparative Example 2 was an embodiment in which 2-hydroxyethyl acrylate was used as a raw material instead of the compound (C), but the final adhesive strength was poor.
• Comparative Example 3 was an embodiment in which the light stabilizer (iii) was not used, but the weather resistance was poor.

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• 2019
  • 2019-03-28 WO PCT/JP2019/013576 patent/WO2019225148A1/ja active Application Filing
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