CN111465671A - Reactive hot-melt adhesive composition, method for producing same, bonding method, image display device, and method for producing same - Google Patents
Reactive hot-melt adhesive composition, method for producing same, bonding method, image display device, and method for producing same Download PDFInfo
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- CN111465671A CN111465671A CN201880080266.8A CN201880080266A CN111465671A CN 111465671 A CN111465671 A CN 111465671A CN 201880080266 A CN201880080266 A CN 201880080266A CN 111465671 A CN111465671 A CN 111465671A
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- 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
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- 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
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C09J175/06—Polyurethanes from polyesters
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- 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
- C09J175/08—Polyurethanes from polyethers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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- Adhesives Or Adhesive Processes (AREA)
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Abstract
The reactive hot melt adhesive composition of the present invention contains a urethane prepolymer having an isocyanate group as a reaction product of a polyol compound and a polyisocyanate compound, and the polyol compound contains a crystalline polyester polyol in an amount of 50 mass% or more based on the total mass of the polyol compound.
Description
Technical Field
The present invention relates to a reactive hot-melt adhesive composition and a method for producing the same, an adhesion method, and an image display device and a method for producing the same.
Background
The reactive hot melt adhesive is a solvent-free adhesive, and therefore, it is less likely to cause a load on the environment and the human body, and can be bonded in a short time, and therefore, it is an adhesive suitable for improving productivity. The reactive hot-melt adhesive contains a reactive resin as a main component, and can exhibit high adhesive strength and the like by increasing the molecular weight thereof through a chemical reaction. As the reactive resin, a urethane prepolymer having an isocyanate group is used (for example, see patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: japanese Kokai publication No. 2008-500406
Patent document 2: international publication No. 2016/157614
Disclosure of Invention
Technical problem to be solved by the invention
The reactive hot-melt adhesive exhibits a certain degree of adhesive strength in a short time by cooling and solidifying the adhesive itself after being applied to an adherend. Then, the isocyanate group of the urethane prepolymer reacts with moisture in the air or on the surface of the adherend to increase the molecular weight thereof, and the isocyanate group is crosslinked to form an adhesive layer, thereby exhibiting excellent adhesive strength. However, the adhesive bonding with the reactive hot melt adhesive does not undergo a high molecular weight and crosslinking immediately after application, and thus the initial adhesive strength on the substrate may be insufficient. Therefore, the reactive hot melt adhesive is required to exhibit excellent initial adhesion strength in a short time, i.e., to be quickly curable.
The purpose of the present invention is to provide a reactive hot-melt adhesive composition having quick curability, a method for producing the same, a bonding method using the reactive hot-melt adhesive composition, an image display device, and a method for producing the same.
Means for solving the problems
The present invention provides a reactive hot melt adhesive composition containing a urethane prepolymer having an isocyanate group as a reaction product of a polyol compound and a polyisocyanate compound, wherein the polyol compound contains 50 mass% or more of a crystalline polyester polyol based on the total mass of the polyol compound. The reactive hot melt adhesive composition of the present invention contains a urethane prepolymer having a structural unit derived from a polyol compound and a structural unit derived from a polyisocyanate compound, wherein 50% by mass or more of the structural units derived from the polyol compound are structural units derived from a crystalline polyester polyol.
The polyol compound may further contain 50 to 90 mass% of a crystalline polyester polyol. The crystalline polyester polyol may also have a structure based on a polycarboxylic acid having 6 to 12 carbon atoms and a polyol having 4 to 10 carbon atoms. The polyol compound may further contain a polyether polyol.
The reactive hot melt adhesive composition of the present invention may further contain a pigment.
The present invention also provides an image display device comprising a flat panel display and a backlight unit, wherein the flat panel display and the backlight unit are bonded to each other by the reactive hot melt adhesive composition of the present invention.
The present invention also provides a method for producing a reactive hot-melt adhesive composition containing a urethane prepolymer having an isocyanate group, comprising a step of reacting a polyol compound with a polyisocyanate compound to obtain a urethane prepolymer having an isocyanate group, wherein the polyol compound contains 50 mass% or more of a crystalline polyester polyol based on the total mass of the polyol compound.
The present invention also provides a method for bonding a flat panel display and a backlight unit, wherein the adhesive layer is formed by using the reactive hot melt adhesive composition of the present invention at a corner between a side surface of the backlight unit and an exposed upper surface of the flat panel display, which is formed by laminating the backlight unit on the upper surface of the flat panel display.
The present invention also provides a method for manufacturing an image display device using the above bonding method.
Effects of the invention
According to the present invention, a reactive hot melt adhesive composition having quick curability, a method for producing the same, a bonding method using the reactive hot melt adhesive composition, an image display device, and a method for producing the same can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing one embodiment of adhesion using the reactive hot melt adhesive composition of the present embodiment.
Detailed Description
The embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.
< definition >
In the present specification, the numerical range represented by "to" means a range including numerical values before and after "to" as a minimum value and a maximum value, respectively. In the numerical ranges recited in the present specification, the upper limit or the lower limit of a certain step may be replaced with the upper limit or the lower limit of another step. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. "a or B" may include either one of a and B, or both of a and B.
[ reactive Hot-melt adhesive composition ]
The reactive hot melt adhesive composition (hereinafter, sometimes simply referred to as "adhesive composition") of the present embodiment contains a urethane prepolymer having an isocyanate group as a reaction product of a polyol compound and a polyisocyanate compound, and the polyol compound contains 50 mass% or more of a crystalline polyester polyol based on the total mass of the polyol compound.
In general, the reactive hot melt adhesive composition can exhibit adhesive strength (final adhesive strength) by reacting with moisture in the air or on the surface of an adherend to increase the molecular weight. The adhesive composition of the present embodiment can exhibit excellent initial adhesion strength in a shorter time than conventional reactive hot melt adhesive compositions, and has excellent rapid curability.
The rapid curability of the adhesive composition of the present embodiment can be evaluated by the following method, for example. The curability of the adhesive composition can be evaluated by applying the adhesive composition to a substrate at room temperature (23 ℃ C., 50% RH) to form an adhesive layer with a width of 1mm, and taking advantage of the time from this point until the tackiness of the surface of the adhesive layer disappears. From the viewpoint of rapid curability, the viscosity is preferably lost within 2 minutes, and more preferably within 1 minute. Here, "tack disappears" means that the sticky feeling disappears when the adhesive layer is touched with a finger.
(urethane prepolymer having isocyanate group)
The urethane prepolymer having an isocyanate group (hereinafter, also referred to as "reactive urethane prepolymer") according to the present embodiment is obtained by reacting a polyol compound containing 50 mass% or more of a crystalline polyester polyol with a polyisocyanate compound, and has an isocyanate group at the end of the urethane prepolymer. Thus, the adhesive composition of the present embodiment can exhibit excellent initial adhesive strength at an early stage.
The polyol compound preferably contains 50 to 90 mass%, more preferably 50 to 85 mass%, and still more preferably 50 to 80 mass% of the crystalline polyester polyol, from the viewpoint of rapid curing and coating workability.
The reactive urethane prepolymer has a structural unit derived from a polyol compound and a structural unit derived from a polyisocyanate compound, and 50 mass% or more of the structural units derived from the polyol compound contain a structural unit derived from a crystalline polyester polyol. The content of the structural unit can be measured by a known analytical method such as NMR and thermal decomposition GC/MS. The structural unit derived from the polyol compound preferably contains 50 to 90 mass%, more preferably 50 to 85 mass%, and still more preferably 50 to 80 mass% of the structural unit derived from the crystalline polyester polyol, from the viewpoint of rapid curing and coating workability.
The crystallinity and amorphousness of the polyester polyol were judged in the state at 25 ℃. Crystallinity can be judged by confirming that the polyester polyol becomes liquid upon heating to 25 ℃ or higher or by confirming the melting temperature of the polyester polyol using a differential scanning calorimeter. In the present specification, as the polyester polyol, a polyester polyol which is crystalline at 25 ℃ is used as the crystalline polyester polyol, and a polyester polyol which is amorphous at 25 ℃ is used as the amorphous polyester polyol. The polyol compound of the present embodiment contains a crystalline polyester polyol as an essential component, but may contain an amorphous polyester polyol as needed.
The polyester polyol may be, for example, a polycondensate of a polyol having 2 to 15 carbon atoms and 2 or 3 hydroxyl groups and a polycarboxylic acid having 2 to 14 carbon atoms (including carbon atoms in the carboxyl group) and having 2 to 6 carboxyl groups. The polyester polyol may be a linear polyester diol formed from a diol and a dicarboxylic acid, or a branched polyester triol formed from a triol and a dicarboxylic acid. In addition, branched polyestertriols can also be obtained by the reaction of diols with tricarboxylic acids.
Examples of the polyhydric alcohol include aliphatic or alicyclic diols such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, respective isomers of butanediol, respective isomers of pentanediol, respective isomers of hexanediol, 2-dimethyl-1, 3-propanediol, 2-methylpropanediol, 1, 6-hexanediol, 2,4, 4-trimethylhexane-1, 6-diol, 2, 4-trimethylhexane-1, 6-diol, 1, 4-cyclohexanediol, and 1, 4-cyclohexanedimethanol; aromatic diols such as 4, 4' -dihydroxydiphenylpropane, bisphenol A, bisphenol F, catechol, resorcinol, and hydroquinone.
Among these, from the viewpoint of easy availability of the crystalline polyester polyol, the polyol is preferably an aliphatic diol, more preferably an aliphatic diol having 2 to 10 carbon atoms, still more preferably an aliphatic diol having 4 to 10 carbon atoms, and yet more preferably an aliphatic diol having 4 to 8 carbon atoms. The polyol is preferably a linear aliphatic diol from the viewpoint of easily obtaining a crystalline polyester polyol having higher crystallinity. The number of carbon atoms of the linear aliphatic diol is preferably 3 to 10, more preferably 4 to 10, further preferably 4 to 8, further preferably 4 to 6, and particularly preferably 5 or 6. The polyhydric alcohol may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the polycarboxylic acid include aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and 1,2, 4-benzenetricarboxylic acid; aliphatic or alicyclic polycarboxylic acids such as maleic acid, fumaric acid, aconitic acid, 1,2, 3-propanetricarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexane-1, 2-dicarboxylic acid, 1, 4-cyclohexadiene-1, 2-dicarboxylic acid and the like.
Among them, from the viewpoint of easy availability of the crystalline polyester polyol, the polycarboxylic acid is preferably an aliphatic dicarboxylic acid, more preferably an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, still more preferably an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, and still more preferably an aliphatic dicarboxylic acid having 6 to 10 carbon atoms. From the viewpoint of easily obtaining a crystalline polyester polyol having higher crystallinity, a linear aliphatic dicarboxylic acid is preferable as the polycarboxylic acid. The number of carbon atoms contained in the linear aliphatic dicarboxylic acid is preferably 4 to 12, more preferably 6 to 12, and still more preferably 6 to 10. The polycarboxylic acid may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The crystalline polyester polyol of the present embodiment particularly preferably has a structure based on a polycarboxylic acid having 6 to 12 carbon atoms and a polyol having 4 to 10 carbon atoms, from the viewpoint of easily obtaining an adhesive composition excellent in rapid curability.
Instead of the polycarboxylic acid, a polycarboxylic acid derivative such as a carboxylic acid anhydride or a compound in which a part of the carboxyl group is esterified may be used. Examples of the polycarboxylic acid derivative include lauryl maleate and stearyl maleate.
The number average molecular weight (Mn) of the crystalline polyester polyol is preferably 500 to 10000, more preferably 1000 to 8000, further preferably 1500 to 6000, and further preferably 2000 to 5500, from the viewpoint of easily obtaining water repellency and high initial adhesive strength.
In the present specification, the number average molecular weight is a value measured by Gel Permeation Chromatography (GPC) and converted to standard polystyrene. GPC measurement can be performed under the following conditions.
Chromatography columns "Gelpack G L A130-S", "Gelpack G L A150-S" and "Gelpack G L A160-S" (a packed column for HP L C, manufactured by Hitachi chemical Co., Ltd.)
Eluent: tetrahydrofuran (THF)
Flow rate of 1.0m L/min
Column temperature: 40 deg.C
RI Detector L-3350 (Hitachi High-Tech Science, product name)
The number average molecular weight of the amorphous polyester polyol is preferably 500 to 3000, more preferably 1000 to 3000, and even more preferably 1500 to 2500, from the viewpoint of improving the initial adhesive strength of the adhesive composition.
The polyol compound of the present embodiment may further contain a polyether polyol. The polyether polyol can adjust the melt viscosity and the usable time (time for which the adhesive composition can be applied) of the adhesive composition after application, and can impart excellent workability, adhesive strength, water resistance, and flexibility to the adhesive composition. From the viewpoint of improving the coating workability of the adhesive composition, polyether glycols are preferred, and examples of the polyether polyols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, and ethylene oxide-modified polypropylene glycol. The polyether polyol may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the polyether polyol is preferably 50% by mass or less, more preferably 10 to 50% by mass, and still more preferably 15 to 50% by mass, based on the total mass of the polyol compounds, from the viewpoints of making it easy to adjust the adhesive composition to a low viscosity and improving the adhesion to an adherend.
The number average molecular weight of the polyether polyol is preferably in the range of 500 to 6000, more preferably in the range of 800 to 5000, and still more preferably in the range of 1000 to 4500, from the viewpoint of easily obtaining adhesive strength and flexibility.
Examples of the polyisocyanate compound include aromatic diisocyanates such as diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and p-phenylene diisocyanate; alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate. The polyisocyanate compound preferably contains an aromatic diisocyanate, more preferably diphenylmethane diisocyanate, from the viewpoint of improving reactivity and adhesive strength. The polyisocyanate compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
In the synthesis of the reactive urethane prepolymer, the mixing ratio of the polyisocyanate compound and the polyol compound is preferably such that the ratio of isocyanate group (NCO) equivalent of the polyisocyanate compound to hydroxyl group (OH) equivalent of the polyol NCO/OH is 1.6 to 3.0, more preferably 1.8 to 2.5. When the NCO/OH ratio is 1.6 or more, the viscosity of the obtained reactive urethane prepolymer tends to be suppressed from increasing, and the workability tends to be easily improved. When the NCO/OH ratio is 3.0 or less, foaming is less likely to occur during the moisture curing reaction of the adhesive composition, and the final adhesive strength can be suppressed from decreasing.
The method for producing the reactive urethane prepolymer is not particularly limited. The adhesive composition may be prepared by mixing a polyisocyanate compound with a polyol compound to synthesize a reactive urethane prepolymer, or may be prepared by synthesizing a reactive urethane prepolymer from a polyisocyanate compound and a polyol compound in advance.
(pigment)
The adhesive composition of the present embodiment may further contain a pigment. The pigment may be appropriately selected depending on the desired characteristics. Examples of the pigment include a black pigment, a white pigment, a red pigment, a yellow pigment, and a blue pigment. The various pigments may be contained in the adhesive composition in an amount selected according to the desired effect, for example, in a range of 0.5 to 30 parts by mass per 100 parts by mass of the urethane prepolymer.
When light-shielding properties are required, a black pigment may be used. Examples of the black pigment include carbon-based black pigments such as carbon black, lampblack, graphite, plant black, and bone black; oxide-based black pigments such as iron oxides, complex oxides of copper and chromium, and complex oxides of copper, chromium, and zinc.
The content of the black pigment is preferably 0.5 to 10 parts by mass, more preferably 0.8 to 8 parts by mass, and further preferably 1 to 5 parts by mass, based on 100 parts by mass of the urethane prepolymer. When the content of the black pigment is 0.5 parts by mass or more, the light-shielding property of the adhesive layer formed of the adhesive composition is easily improved, and when the content of the black pigment is 10 parts by mass or less, the viscosity of the adhesive composition is easily adjusted.
The particle diameter (average primary particle diameter) of the black pigment is not particularly limited, and may be, for example, 1 to 200nm, or 5 to 100 nm. The average primary particle size in the present specification represents a numerical value obtained by the method described in the examples.
When light reflectivity is required, a white pigment may be used. Examples of the white pigment include titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, antimony oxide, and zirconium oxide.
(other Components)
The adhesive composition of the present embodiment may further contain a catalyst, an antioxidant, an ultraviolet absorber, a surfactant, a flame retardant, a filler, and the like in an appropriate amount as needed.
Examples of the catalyst include dibutyltin dilaurate, dibutyltin dioctoate, dimethylcyclohexylamine, dimethylbenzylamine and trioctylamine.
(Properties)
The usable time (time for which the adhesive composition of the present embodiment can be applied) is preferably 120 seconds or less, and more preferably 60 seconds or less. When the pot life is 60 seconds or less, the adhesive strength is likely to be exhibited immediately after the adhesive composition is used for adhesion.
From the viewpoint of improving the applicability to an adherend, the melt viscosity of the adhesive composition of the present embodiment measured using a rotational viscometer can be measured according to JIS Z8803 by the methods described in the examples. The melt viscosity of the adhesive composition is preferably 10 pas or less, more preferably 8 pas or less, and still more preferably 7 pas or less at 120 ℃. The lower limit of the melt viscosity is not limited, and may be, for example, 0.5 pas or more at 120 ℃.
[ method for producing reactive Hot-melt adhesive composition ]
The method for producing an adhesive composition of the present embodiment includes a step of reacting a polyol compound with a polyisocyanate compound to obtain a urethane prepolymer having an isocyanate group, wherein the polyol compound contains 50 mass% or more of a crystalline polyester polyol based on the total mass of the polyol compound.
The adhesive composition of the present embodiment can also be produced by reacting a polyol compound with a polyisocyanate compound to obtain a reactive urethane prepolymer, and then mixing the reactive urethane prepolymer with a component such as a pigment, which is added as needed. Further, the adhesive composition may be prepared by mixing the polyisocyanate compound and the polyol compound with a component such as a pigment, which is blended as necessary, and synthesizing the reactive urethane prepolymer. For example, when a pigment is blended in the adhesive composition, the adhesive composition can be prepared by a step of obtaining a urethane prepolymer by reacting a polyol compound with a polyisocyanate compound in the presence of the pigment; alternatively, the adhesive composition may be prepared by a step of obtaining a urethane prepolymer by reacting a polyol compound with a polyisocyanate compound in advance, and then mixing the urethane prepolymer with a pigment.
Various adherends can be bonded by using the reactive hot melt adhesive composition of the present embodiment. The adhesive composition of the present embodiment can bond adherends to each other by applying the adhesive composition to the surface or side surface of the adherends, and can exhibit excellent initial adhesion strength in a shorter period of time than conventional reactive hot-melt adhesive compositions.
Examples of the adherend include a metal adherend (SUS, aluminum, and the like) and a nonmetal adherend (polycarbonate, glass, and the like). The adhesive composition of the present embodiment exhibits excellent adhesive strength not only to a non-metal adherend but also to a metal adherend. The adhesive composition of the present embodiment can also be used for bonding a flat panel display such as a liquid crystal display using a double-sided tape in the related art to a backlight unit.
The flat panel display is a thin image display having a flat screen and is a liquid crystal display, a plasma display, an organic E L display, an FED (field emission display), an electronic paper, or the like.
A method for bonding a flat panel display and a backlight unit using the adhesive composition of the present embodiment will be described below. Fig. 1 is a schematic cross-sectional view showing one embodiment of adhesion using the adhesive composition of the present embodiment.
The flat panel display 10 and the backlight unit 20 are stacked to form a two-layer structure, and the adhesive layer 30 is formed by applying an adhesive composition to the corners between the side surfaces of the backlight unit 20 and the exposed upper surface of the flat panel display 10, whereby the flat panel display 10 and the backlight unit 20 can be bonded to each other. That is, in the bonding method of the present embodiment, the adhesive composition of the present embodiment is used in the corner between the side surface of the backlight unit 20 and the exposed upper surface of the flat panel display 10, which is formed by laminating the backlight unit 20 on the upper surface of the flat panel display 10, to form the adhesive layer 30. By using the above bonding method, an image display device including a flat panel display and a backlight unit can be manufactured. The adhesive composition of the present embodiment is preferably used in the method for manufacturing an image display device, from the viewpoint of enhancing the efficiency of the manufacturing process, because it has a high curing rate. In this case, when an adhesive composition containing a black pigment is used, adhesion and light shielding can be performed simultaneously. In the case of the bonding method according to the present embodiment, the thickness can be reduced as compared with a conventional method in which the end portion of the flat panel display and the end portion of the backlight unit are bonded by a double-sided tape. When the adhesive composition of the present embodiment is bonded by the above bonding method, it can be used for bonding a two-layer adherend as described in the above bonding embodiment, and can also be used for bonding an adherend having three or more layers.
The adhesive composition of the present embodiment is particularly preferable for the above bonding method because of its quick curability.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
(polyol compound)
PES-1 (polyester polyol obtained by reacting adipic acid and 1, 6-hexanediol, number of hydroxyl groups: 2, Mn: 3000) and PES-2 (polyester polyol obtained by reacting sebacic acid and 1, 6-hexanediol, number of hydroxyl groups: 2, Mn: 5000) were prepared as crystalline polyester polyols, PES-3 (polyester polyol obtained by reacting adipic acid and ethylene glycol, number of hydroxyl groups: 2, Mn: 2000) was prepared as polyether polyol, and PP2000 (polypropylene glycol, Mn: 2000, Asahi glass company, "EXENO L2020") was prepared as crystalline polyester polyols.
(polyisocyanate Compound)
MDI (diphenylmethane diisocyanate, the number of isocyanate groups: 2, "Millionote MT" available from TOSOH corporation) was prepared as the polyisocyanate compound.
(pigment)
As black pigments, carbon black A (particle diameter: 30 to 50nm), carbon black B (particle diameter: 20 to 30nm) and carbon black C (particle diameter: 10 to 20nm) were prepared, wherein the particle diameters represent average primary particle diameters, and the carbon black was observed with a scanning electron microscope ("X L-30" manufactured by Philips corporation), and from the obtained observation images, the major diameters of 50 primary particles of the carbon black were measured, and the average value thereof was defined as the average primary particle diameter.
(example 1)
50 parts by mass of PES-1 dehydrated in advance by a vacuum dryer, 50 parts by mass of PP2000, 21.1 parts by mass of MDI, and 3 parts by mass of carbon black A were mixed, and then they were reacted at 110 ℃ for 2 hours, and further, they were stirred under reduced pressure at 110 ℃ for 2 hours under deaeration, to obtain an adhesive composition containing a urethane prepolymer having an isocyanate group and a black pigment.
(examples 2 to 8, comparative examples 1 to 2)
Adhesive compositions were obtained in the same manner as in example 1, except that the kinds and blending amounts of the respective components were changed as shown in table 1. In addition, the numbers in table 1 refer to parts by mass.
TABLE 1
The adhesive compositions prepared in examples and comparative examples were evaluated for their respective properties as follows. The results are shown in Table 2.
(melt viscosity)
The melt viscosity of the adhesive composition (sample amount: 15g) was measured at a rotor rotation speed of 50rpm at 120 ℃ using a type B viscometer ("TVB-25H" manufactured by Toyobo industries Co., Ltd.) according to JIS Z8803 using a No. 4 rotor.
(curing Property)
The adhesive composition was applied to a substrate at room temperature (23 ℃ C., 50% RH) to form an adhesive layer with a width of 1mm, and the time from this time to the disappearance of the tackiness on the surface of the adhesive layer was measured to determine the curability. The case where the viscosity disappeared within 1 minute was evaluated as "a", the case where the viscosity disappeared within more than 1 minute and within 2 minutes was evaluated as "B", and the case where the viscosity did not disappear within 2 minutes was evaluated as "C".
(adhesion)
An adhesive composition was melted at 100 ℃ to form an adhesive layer of 12.5mm × and 25mm × mm in length and 0.1mm in thickness on a polycarbonate sheet of 100mm × in length and 25mm × mm in thickness and 2mm in thickness under an environment of 25 ℃ temperature and 50% humidity, and then a polycarbonate sheet of 100mm × mm in length and 25mm in width × mm in thickness and 2mm in thickness was pressure-bonded to the adhesive layer to prepare a test piece ("Autograph AGS-1 kNX" manufactured by Shimadzu corporation) according to JIS6850, and after 10 minutes from this point and 30 minutes from this point, a shear adhesion test (peel rate: 10 mm/minute) of the test piece was performed, and the initial adhesion strength was measured.
(spitting Property)
The adhesive composition was melted at 100 ℃ and put into a syringe container (PSY-30E manufactured by Musashi-engineering Co., Ltd.) equipped with a precision nozzle (SHN-0.25N manufactured by Musashi-engineering Co., Ltd.) having an inner diameter of 0.25mm, and sprayed out at a pressure of 300kPa using a dispenser (SHOTMASTER 200DS manufactured by Musashi-engineering Co., Ltd.) heated to 100 ℃ in advance. The case where the discharge was realized was evaluated as "a", and the case where the discharge was not possible was evaluated as "C".
(light-shielding property)
The adhesive composition was melted at 100 ℃ to prepare a test piece having a length of 15mm × and a width of 40mm × and a thickness of 0.1mm, and the test piece was allowed to stand in a thermostatic bath at 25 ℃ and 50% RH for 7 days, and then the OD value was measured by a transmission densitometer ("TM-5" manufactured by Ishigo electronics Co., Ltd.).
TABLE 2
The adhesive compositions obtained in examples 1 to 8 were confirmed to have excellent quick curability and to exhibit adhesive strength in a short time.
Description of the symbols
10 flat panel display, 20 backlight unit, 30 adhesive layer.
Claims (13)
1. A reactive hot-melt adhesive composition comprising an isocyanate group-containing urethane prepolymer which is a reaction product of a polyol compound and a polyisocyanate compound, wherein the polyol compound contains 50 mass% or more of a crystalline polyester polyol based on the total mass of the polyol compound.
2. The reactive hot melt adhesive composition according to claim 1, wherein the polyol compound contains 50 to 90 mass% of the crystalline polyester polyol.
3. The reactive hot melt adhesive composition according to claim 1 or 2, wherein the crystalline polyester polyol has a structure based on a polycarboxylic acid having 6 to 12 carbon atoms and a polyol having 4 to 10 carbon atoms.
4. The reactive hot melt adhesive composition of any one of claims 1 to 3, wherein the polyol compound comprises a polyether polyol.
5. A reactive hot-melt adhesive composition comprising a urethane prepolymer having a structural unit derived from a polyol compound and a structural unit derived from a polyisocyanate compound, wherein 50% by mass or more of the structural units derived from the polyol compound are structural units derived from a crystalline polyester polyol.
6. The reactive hot melt adhesive composition according to any one of claims 1 to 5, further comprising a pigment.
7. An image display device comprising a flat panel display and a backlight unit,
bonding the flat panel display and the backlight unit using the reactive hot melt adhesive composition of any one of claims 1 to 6.
8. A process for producing a reactive hot-melt adhesive composition containing a urethane prepolymer having an isocyanate group,
which comprises a step of reacting a polyol compound with a polyisocyanate compound to obtain the urethane prepolymer having an isocyanate group,
the polyol compound contains 50 mass% or more of a crystalline polyester polyol based on the total mass of the polyol compound.
9. The production method according to claim 8, wherein the polyol compound contains 50 to 90 mass% of the crystalline polyester polyol.
10. The production method according to claim 8 or 9, wherein the crystalline polyester polyol has a structure based on a polycarboxylic acid having 6 to 12 carbon atoms and a polyol having 4 to 10 carbon atoms.
11. The production method according to any one of claims 8 to 10, wherein the polyol compound comprises a polyether polyol.
12. A method of bonding a flat panel display and a backlight unit, wherein the adhesive layer is formed by using the reactive hot melt adhesive composition according to any one of claims 1 to 6 at a corner between a side surface of the backlight unit and an exposed upper surface of the flat panel display, the corner being formed by laminating the backlight unit on the upper surface of the flat panel display.
13. A method for manufacturing an image display device, which comprises using the bonding method according to claim 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-244037 | 2017-12-20 | ||
| JP2017244037 | 2017-12-20 | ||
| PCT/JP2018/046156 WO2019124266A1 (en) | 2017-12-20 | 2018-12-14 | Reactive hot-melt adhesive composition and method for manufacturing same, bonding method, and image display device and method for manufacturing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111465671A true CN111465671A (en) | 2020-07-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880080266.8A Pending CN111465671A (en) | 2017-12-20 | 2018-12-14 | Reactive hot-melt adhesive composition, method for producing same, bonding method, image display device, and method for producing same |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP7415559B2 (en) |
| KR (1) | KR20200100052A (en) |
| CN (1) | CN111465671A (en) |
| PH (1) | PH12020550931A1 (en) |
| TW (1) | TW201930530A (en) |
| WO (1) | WO2019124266A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7380842B2 (en) * | 2021-02-02 | 2023-11-15 | Dic株式会社 | Adhesives, laminates, packaging materials |
| WO2024009958A1 (en) * | 2022-07-04 | 2024-01-11 | 積水化学工業株式会社 | Reactive hot melt resin composition, cured product, use of reactive hot melt resin composition, and end face protection method |
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| JPH07118622A (en) * | 1993-10-27 | 1995-05-09 | Sekisui Chem Co Ltd | Hot-melt adhesive composition |
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| JP2008500406A (en) | 2004-05-24 | 2008-01-10 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレーション | New reactive hot melt adhesive |
| JP4688658B2 (en) | 2005-12-06 | 2011-05-25 | 日東電工株式会社 | Shading adhesive sheet |
| JP2008094960A (en) * | 2006-10-12 | 2008-04-24 | Aica Kogyo Co Ltd | Moisture-curable reactive hot melt adhesive |
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- 2018-12-14 KR KR1020207016084A patent/KR20200100052A/en not_active IP Right Cessation
- 2018-12-14 JP JP2019561051A patent/JP7415559B2/en active Active
- 2018-12-14 WO PCT/JP2018/046156 patent/WO2019124266A1/en active Application Filing
- 2018-12-14 CN CN201880080266.8A patent/CN111465671A/en active Pending
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| Publication number | Publication date |
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| TW201930530A (en) | 2019-08-01 |
| KR20200100052A (en) | 2020-08-25 |
| JPWO2019124266A1 (en) | 2021-01-21 |
| JP7415559B2 (en) | 2024-01-17 |
| WO2019124266A1 (en) | 2019-06-27 |
| PH12020550931A1 (en) | 2021-05-10 |
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