WO2016163232A1 - 層間充填用硬化性樹脂組成物 - Google Patents

層間充填用硬化性樹脂組成物 Download PDF

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WO2016163232A1
WO2016163232A1 PCT/JP2016/059141 JP2016059141W WO2016163232A1 WO 2016163232 A1 WO2016163232 A1 WO 2016163232A1 JP 2016059141 W JP2016059141 W JP 2016059141W WO 2016163232 A1 WO2016163232 A1 WO 2016163232A1
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meth
acrylate
active energy
urethane
energy ray
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PCT/JP2016/059141
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English (en)
French (fr)
Japanese (ja)
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相模貴雄
山下亮
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ダイセル・オルネクス株式会社
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Priority to KR1020177030264A priority Critical patent/KR102418173B1/ko
Priority to CN201680019420.1A priority patent/CN107406563B/zh
Publication of WO2016163232A1 publication Critical patent/WO2016163232A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal 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
    • 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
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks

Definitions

  • the present invention has an active energy ray-curable composition that can be used as an interlayer filler for transparent substrates for displays such as personal computers, televisions, and mobile phones, and a cured product layer of the active energy ray-curable composition. It relates to a laminate.
  • This application claims the priority of Japanese Patent Application No. 2015-0778067 for which it applied to Japan on April 6, 2015, and uses the content here.
  • ⁇ Displays used in personal computers, car navigation systems, TVs, mobile phones, etc., display images with light from the backlight.
  • Various transparent substrates such as glass substrates such as glass plates and plastic substrates such as plastic films, including color filters, are used for displays, and the effects of light scattering and absorption of these transparent substrates are used.
  • the amount of light output from the light source to the outside of the display is reduced. If this decrease width becomes large, the screen becomes dark and the visibility decreases. In order to improve the visibility, it is possible to increase the antireflection property of the display surface layer or increase the amount of light from the light source.
  • Performance required for the resin used between layers of transparent substrates such as glass substrates and plastic substrates is not only high adhesion to transparent substrates, but also high deformation resistance and high flexibility, as well as high transparency
  • the transmittance at 400 nm is required to be 95% or more. Further, it is necessary that resistance at high temperatures, specifically, no change in shape at 95 ° C. or no change in hue. Aiming at a resin having such performance, urethane (meth) acrylates using an olefin skeleton and compositions containing these have been proposed in the following prior art documents.
  • Japanese Patent No. 1041553 Japanese Patent No. 2582575 JP 2002-069138 A JP 2002-309185 A JP 2003-155455 A JP 2010-144000 A JP 2010-254890 A JP 2010-254891 A JP 2010-265402 A JP 2011-116965 A
  • urethane (meth) acrylates described in these prior documents and compositions containing them cannot be produced on a large scale because of the increased viscosity during the synthesis of urethane (meth) acrylate, and the reaction
  • the resulting urethane (meth) acrylate and these compositions become cloudy at low temperatures, resulting in poor transparency, and the cured coating changes shape at high temperatures. Therefore, it was insufficient as an interlayer filler for a transparent substrate for display.
  • thinning of the base material is required, and further reduction in curing shrinkage of the active energy ray curable composition used as an interlayer filler is required. Yes.
  • durability under high temperature is required. In this case, adhesion retention between the cured interlayer filler and the substrate is required.
  • the object of the present invention is to cure the active energy ray that can produce the target component without increasing the viscosity when producing the component of the active energy ray curable composition, and with fewer by-products.
  • An active energy ray-curable composition that can be used as an interlayer filler even if it is a thin base material for smartphones and tablets due to its low curing shrinkage.
  • the cured product of the active energy ray-curable composition exhibits high-temperature heat resistance in addition to high flexibility and high transparency, and an active energy ray-curable composition having high adhesion retention with a substrate, and the active energy It is providing the laminated body which has a hardened
  • the present invention relates to a polyolefin polyol (A) having a polyolefin skeleton, an aliphatic alcohol (B) having three or more hydroxyl groups and a molecular weight of 100 or more and less than 800, an aliphatic diisocyanate (C), Is subjected to a urethanation reaction to form a urethane isocyanate prepolymer containing an isocyanate group, and then the urethane isocyanate prepolymer, a (meth) acrylate (D) having a hydroxyl group, and an alcohol (E) having one hydroxyl group.
  • A polyolefin polyol
  • B aliphatic alcohol
  • C aliphatic diisocyanate
  • Urethane (meth) acrylate (X) obtained by reacting with An active energy ray-curable composition
  • An active energy ray-curable composition comprising a monofunctional (meth) acrylate (Y) and a photopolymerization initiator (Z)
  • the polyolefin-based polyol (A) having a polyolefin skeleton is at least one selected from the group consisting of polybutadienes having hydroxyl groups at both ends, polyisoprene, and polyols obtained by hydrogenating these, and the weight average molecular weight is 2, 000 to 10,000
  • an active energy ray-curable composition having a (meth) acryloyl group concentration of urethane (meth) acrylate (X) of 0.05 or more and less than 0.20 mol / kg.
  • the reaction is continued until the isocyanate group concentration in the reaction liquid when forming the urethane isocyanate prepolymer containing the isocyanate group is equal to or lower than the remaining isocyanate group concentration when all of the hydroxyl groups subjected to the reaction are urethanized. It is preferable to make it.
  • cured material layer of the said active energy ray curable composition is provided between the 1st transparent base material chosen from glass and a plastics, and the 2nd transparent base material chosen from glass and a plastics.
  • the laminated body which has is also demonstrated.
  • the said laminated body apply
  • a laminate obtained by attaching a transparent substrate and then irradiating active energy rays to cure the active energy ray-curable composition to form a cured product layer will also be described.
  • a urethane isocyanate prepolymer containing an isocyanate group After reacting to form a urethane isocyanate prepolymer containing an isocyanate group, the urethane isocyanate prepolymer, a (meth) acrylate (D) having a hydroxyl group, and an alcohol (E) having one hydroxyl group
  • Urethane (meth) acrylate (X) obtained by An active energy ray-curable composition comprising a monofunctional (meth) acrylate (Y) and a photopolymerization initiator (Z),
  • the polyolefin-based polyol (A) having a polyolefin skeleton is at least one selected from the group consisting of polybutadienes having hydroxyl groups at both ends, polyisoprene, and polyols obtained by hydrogenating these, and the weight average molecular weight is 2, 000 to 10,000
  • An active energy ray-curable composition having a (meth) acryloyl group concentration of urethane (meth) acrylate (X) of 0.05 or more and less than 0.20 mol / kg.
  • Mw weight average molecular weight
  • the alcohol (B) is at least one selected from the group consisting of trimethylolpropane, pentaerythritol, glycerin, and modified compounds thereof. Composition.
  • the amount of the alcohol (B) used is, for example, 0.01 to 3% by weight, preferably 0.1 to 3% by weight with respect to the total amount of urethane (meth) acrylate-containing product obtained (100% by weight).
  • the active energy ray-curable composition according to any one of [1] to [3], which is 1% by weight, more preferably 0.3 to 0.6% by weight.
  • the diisocyanate (C) is at least one selected from the group consisting of alicyclic diisocyanates, linear or branched aliphatic diisocyanates, and diisocyanate compounds obtained by hydrogenating aromatic isocyanates.
  • the active energy ray-curable composition according to any one of [1] to [4].
  • the (meth) acrylate (D) has one (meth) acryloyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxynormalpropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.
  • [1] to [5] which are (meth) acrylates having two or more (meth) acryloyl groups such as (meth) acrylate having a hydroxyl group or pentaallythritol triacrylate and further having a hydroxyl group.
  • the active energy ray-curable composition according to any one of the above.
  • the alcohol (E) is an aliphatic or alicyclic primary alcohol having 3 or more carbon atoms, and the molecular weight thereof is in the range of 70 to 400.
  • the use concentration of (meth) acrylate (Y) is, for example, 20 to 60% by weight, preferably 20 to 40% with respect to the total amount of urethane (meth) acrylate-containing product (100% by weight) obtained.
  • the active energy ray-curable composition according to any one of [1] to [7], which is wt%.
  • a resin layer is formed by applying any one of the active energy ray-curable compositions according to any one of [1] to [9] on a first transparent substrate, and the resin layer The laminated body obtained by making a 2nd transparent base material adhere on it, and then irradiating an active energy ray, hardening the said active energy ray curable composition, and forming a hardened
  • the active energy ray-curable composition of the present invention is not intended to increase the viscosity during the production of the urethane (meth) acrylate (X), which is a component, and the by-product of the by-product is small, and is intended. Urethane (meth) acrylate can be produced.
  • the active energy ray-curable composition (before curing) of the present invention does not deteriorate the appearance of the resin due to white turbidity at low temperatures.
  • the active energy ray-curable composition of the present invention has good wettability with a glass substrate or a plastic substrate, high flexibility, high heat resistance, and low cure shrinkage, so that it is a smartphone or tablet.
  • the active energy ray curable composition of this invention is used as an interlayer filler, the adhesiveness retention of the hardened
  • the active energy ray-curable composition of the present invention is filled between transparent substrates of displays used in personal computers, car navigation systems, televisions, mobile phones (smartphones), tablets, etc. It is useful in that it can prevent light scattering in the layer and can obtain a laminate that hardly undergoes a hue change or a shape change during a heat resistance test.
  • the urethane (meth) acrylate (X) used in the present invention is a urethanization reaction of a polyolefin polyol (A) having a specific polyolefin skeleton, a specific aliphatic alcohol (B), and an aliphatic diisocyanate (C). After forming a urethane isocyanate prepolymer containing an isocyanate group, the urethane isocyanate prepolymer, a (meth) acrylate (D) having a hydroxyl group, and an alcohol (E) having one hydroxyl group are reacted. Can be manufactured.
  • monofunctional (meth) acrylate (Y) may be used as a compatibilizing agent when forming a urethane isocyanate prepolymer containing an isocyanate group. good.
  • the urethane (meth) acrylate (X) is simply “urethane (meth) acrylate (X)” or “(X)”, and the polyolefin polyol (A) having a polyolefin skeleton is simply “polyol (A)” or “(A)” and an aliphatic alcohol (B) having three or more hydroxyl groups and a molecular weight of 100 to less than 800 are simply referred to as “alcohol (B)” or “(B)” and an aliphatic diisocyanate ( C) is simply “diisocyanate (C)” or “(C)” and (meth) acrylate (D) having a hydroxyl group is simply “(meth) acrylate (D)” or “(D)” and one hydroxyl group Alcohol (E) having the following is simply “alcohol (E)” or “(E)” and “urethane isocyanate prepolymer containing isocyanate groups” is simply “
  • a method for producing the urethane (meth) acrylate (X) of the present invention for example, “a method in which (A), (B), (C), (D), and (E) are mixed and reacted” or “( C), (D) and (E) are polymerized, and compared with conventional methods such as “method of reacting the polymer with (A) and (B)”, preventing increase in viscosity, resin appearance, and by-products There is an effect that the suppression, transparency of the cured product, heat resistance and the like are remarkably improved.
  • urethane (meth) acrylate formed by “a method in which (A), (B), (C), (D) and (E) are mixed and reacted” is highly viscous, Stirring becomes difficult.
  • the urethanization reaction proceeds non-uniformly, not only is there a high possibility that gelation will occur partially, but urethane (meth) acrylate (by-product) that does not contain polyol (A) in the skeleton is generated and transmitted. It causes a decrease in rate and flexibility.
  • various urethane (meth) acrylates are produced, quality control becomes difficult when used as an active energy ray-curable composition.
  • Examples of the urethane isocyanate prepolymer forming method (synthesis method) in the method for producing urethane (meth) acrylate (X) of the present invention include the following methods 1 to 3.
  • [Method 1] A method in which polyol (A), alcohol (B), and diisocyanate (C) are mixed and reacted.
  • [Method 2] A method of reacting the diisocyanate (C) while adding the polyol (A) and the alcohol (B) dropwise.
  • Methodhod 3 A method of reacting the diisocyanate (C) dropwise into the polyol (A) and the alcohol (B).
  • urethane (meth) acrylate obtained by reacting (meth) acrylate (D) and alcohol (E) has a low acrylic density, so the cured product has a sufficient crosslinking density. Cannot be obtained.
  • [Method 1] and [Method 2] are particularly preferably used in order to obtain the desired urethane isocyanate prepolymer in good yield.
  • the polyol (A) and the alcohol (B) are first charged in the reactor and stirred until uniform, and then the diisocyanate (C) is charged and made uniform. This makes it possible to keep the viscosity of the reaction solution low. Thereafter, a method of starting urethanization by adding a urethanization catalyst after raising the temperature as necessary while stirring is desirable. The temperature may be increased as necessary after adding the urethanization catalyst.
  • the urethanization catalyst When the urethanization catalyst is added before the polyol (A), alcohol (B) and isocyanate (C) are uniformly stirred, the urethane prepolymer obtained is gelled by the urethanation reaction proceeding non-uniformly. Problems arise. Furthermore, the reaction may be terminated with unreacted diisocyanate (C) remaining in the system. In this case, the transmittance at 400 nm is lowered due to the by-product obtained by the reaction between the (meth) acrylate (D) and alcohol (E) to be reacted later and the remaining diisocyanate (C), which is not preferable.
  • the content of such by-products is preferably less than 7% by weight with respect to the target urethane isocyanate prepolymer. If it is 7% by weight or more, the transmittance at 400 nm is lowered.
  • Method 1 is industrial in that the polyol (A) having a high viscosity and the alcohol (B) that may be a solid may be charged directly into the reactor, and the urethane (meth) acrylate (X) can be produced in one pot. Is excellent.
  • (meth) acrylate (Y) may be used as a compatibilizing agent.
  • the polyol (A) and the alcohol (B) are charged into the reactor together with the (meth) acrylate (Y) and stirred until uniform, and then the diisocyanate (C) is charged and made uniform.
  • the viscosity of the reaction solution can be further reduced.
  • a method of starting urethanization by adding a urethanization catalyst after raising the temperature as necessary while stirring is desirable. The temperature may be increased as necessary after adding the urethanization catalyst.
  • a urethane isocyanate prepolymer is synthesized (formed) by reaction with polyol (A), alcohol (B) and diisocyanate (C)
  • the reaction is continued until all hydroxyl groups in the reaction solution are urethanized. It is preferable to carry out. That is, it is preferable to carry out the reaction until the isocyanate group concentration in the reaction liquid at the time of forming the urethane isocyanate prepolymer is equal to or lower than the remaining isocyanate group concentration when all the hydroxyl groups subjected to the reaction are urethaned.
  • the end point of the reaction is the measurement of the isocyanate group concentration in the reaction solution, and all of the hydroxyl groups charged into the system were below the isocyanate group concentration when urethane was converted, the isocyanate group concentration no longer changed, etc. Can be confirmed.
  • the molar ratio of the hydroxyl group (total amount) of the polyol (A) and the alcohol (B) and the isocyanate group of the diisocyanate (C) is not particularly limited. 1 to 2.0 mol, preferably 1.1 to 1.4 mol, more preferably 1.17 to 1.38 mol can be used.
  • the reaction is performed so that the number of moles of hydroxyl group of (meth) acrylate (D) having a hydroxyl group is excessive with respect to the number of moles of isocyanate group of the urethane isocyanate prepolymer, and The reaction must be continued until the residual isocyanate group concentration in the reaction solution reaches 0.05% by weight or less.
  • the total number of moles of hydroxyl groups of (meth) acrylate (D) and alcohol (E) having a hydroxyl group is 1.0 to 1 with respect to 1 mole of the isocyanate group of the urethane isocyanate prepolymer. 0.1 mol, preferably 1.0 to 1.05 mol.
  • This reaction is preferably performed in the presence of a polymerization inhibitor such as dibutylhydroxytoluene, hydroquinone, hydroquinone monomethyl ether, or phenothiazine for the purpose of preventing polymerization.
  • a polymerization inhibitor such as dibutylhydroxytoluene, hydroquinone, hydroquinone monomethyl ether, or phenothiazine for the purpose of preventing polymerization.
  • the addition amount of these polymerization inhibitors is preferably 1 to 10,000 ppm (weight basis), more preferably 100 to 1000 ppm, and still more preferably 400 to 1000 ppm with respect to the urethane (meth) acrylate (X) to be produced. If the addition amount of the polymerization inhibitor is less than 1 ppm relative to the urethane (meth) acrylate (X), a sufficient polymerization inhibition effect may not be obtained. If it exceeds 10000 ppm, the physical properties of the product may be adversely affected. There is.
  • ⁇ Atmosphere> In the manufacturing method of urethane (meth) acrylate (X) of this invention, it is preferable to carry out in molecular oxygen containing gas atmosphere.
  • the oxygen concentration is appropriately selected in consideration of safety.
  • a catalyst may be used in order to obtain a sufficient reaction rate.
  • the catalyst dibutyltin dilaurate, tin octylate, tin chloride or the like can be used, but dibutyltin dilaurate is preferable from the viewpoint of reaction rate.
  • the amount of these catalysts added is usually 1 to 3000 ppm (weight basis), preferably 50 to 1000 ppm, based on the urethane (meth) acrylate (X) to be produced. When the addition amount of the catalyst is less than 1 ppm, a sufficient reaction rate may not be obtained. When the addition amount is more than 3000 ppm, there is a risk of adversely affecting various physical properties of the product such as a decrease in light resistance.
  • the urethane (meth) acrylate (X) of the present invention can be produced in the presence of a known volatile organic solvent.
  • the volatile organic solvent can be distilled off under reduced pressure after the production of urethane (meth) acrylate (X).
  • the volatile organic solvent remaining in the composition can be applied to a transparent substrate and then removed by drying.
  • a volatile organic solvent means the organic solvent whose boiling point does not exceed 200 degreeC.
  • the active energy ray-curable composition of the present invention may or may not contain the organic solvent used in the production of urethane (meth) acrylate (X). It should be noted that it is preferable not to use any volatile organic solvent in the sealed curing system from the production of urethane (meth) acrylate (X) to the preparation of the active energy ray curable composition. In this case, it is preferable that the active energy ray-curable composition of the present invention does not contain a volatile organic solvent.
  • “not contained” means that the proportion of the entire active energy ray-curable composition is 1% by weight or less, preferably 0.5% by weight or less. More preferably, it is 1% by weight or less.
  • reaction temperature In the method for producing urethane (meth) acrylate (X) of the present invention, the reaction is preferably carried out at a temperature of 130 ° C. or less, more preferably 40 to 130 ° C. When the temperature is lower than 40 ° C., a practically sufficient reaction rate may not be obtained. When the temperature is higher than 130 ° C., the double bond portion may be cross-linked by radical polymerization due to heat, and a gelled product may be generated.
  • the isocyanate group concentration in the reaction solution is the remaining isocyanate group concentration when all of the hydroxyl groups subjected to the reaction are urethanated. It is preferable to make it react until it becomes the following, and to form a urethane isocyanate prepolymer.
  • the residual isocyanate group concentration can be analyzed by gas chromatography, titration method or the like.
  • the isocyanate group concentration in the reaction solution when forming urethane (meth) acrylate (X) from the urethane isocyanate prepolymer is usually carried out until the residual isocyanate group is 0.1% by weight or less.
  • the residual isocyanate group concentration is analyzed by gas chromatography, titration method or the like.
  • a part of the terminal (meth) acryloyl group may be modified to an alkoxy group.
  • wettability with a substrate can be adjusted.
  • the (meth) acryloyl group concentration of urethane (meth) acrylate (X) (hereinafter sometimes simply referred to as “(meth) acryloyl group concentration”) can be calculated by applying the following formula. .
  • the number of (meth) acryloyl groups in (meth) acrylate (D) is “1” for 2-hydroxyethyl acrylate, and the number of (meth) acryloyl groups for pentaerythritol triacrylate is “3”.
  • the necessary (meth) acryloyl group concentration is 0.05 or more and less than 0.20 mol / kg, preferably 0.06 to 0.16 mol / kg or less.
  • the (meth) acryloyl group concentration is less than 0.05 mol / kg, there is a risk of insufficient curing even when irradiated with active energy rays, and the initial adhesion to the substrate is reduced due to a decrease in cohesive strength. This is not preferable.
  • the (meth) acryloyl group concentration is 0.20 mol / kg or more, the heat resistance of the cured product is lowered, which is not preferable.
  • the cured product is tested under the conditions of 95 ° C. and 1000 hours, the hardness of the coating film is increased, the adhesion with the substrate is decreased, and the shrinkage of the curing is caused. It is a problem that causes the coating shape to change.
  • Alcohol (E) is reacted with urethane isocyanate prepolymer to make the desired proportion of the end of urethane isocyanate prepolymer an alkoxy group, and then (meth) acrylate (D) is reacted to the remaining isocyanate group.
  • the urethane isocyanate prepolymer is reacted with (meth) acrylate (D) to make the desired proportion of the end of the urethane isocyanate prepolymer a (meth) acryloyl group, and then reacted with alcohol (E) to remain.
  • a method of introducing an alkoxy group into an isocyanate group (3) A method in which (meth) acrylate (D) and alcohol (E) are simultaneously reacted with a urethane isocyanate prepolymer to introduce a desired proportion of alkoxy groups and (meth) acryloyl groups at the ends of the urethane isocyanate prepolymer. . (4) A method combining the methods (1) to (3).
  • the polyolefin-based polyol (A) having a polyolefin skeleton is not particularly limited as long as it is a polyol having a polyolefin skeleton and having two or more hydroxyl groups, but polybutadiene, polyisoprene having hydroxyl groups at both ends, and hydrogen
  • the polyol is at least one selected from the group consisting of a modified polyol and has a weight average molecular weight of 2,000 to 10,000.
  • the weight average molecular weight (Mw) of the polyolefin-based polyol (A) having a polyolefin skeleton may be in the range of 2,000 to 10,000, but is preferably 2,000 to 6,000.
  • the weight average molecular weight (Mw) is a value in terms of polystyrene as measured by GPC. If the Mw is less than 2,000, the resin Tg after urethane (meth) acrylate conversion is increased, the flexibility is lowered, the resin appearance is deteriorated, and the by-products are sometimes increased. On the other hand, when Mw exceeds 10,000, the crosslinking density becomes too small, which may cause deterioration in curability and change in shape at high temperature.
  • the crosslink density can be increased by adding a polyfunctional (meth) acrylate, but if a polyfunctional monomer is added as will be described later, it causes a poor appearance under an environmental test.
  • polyol (A) As the polyol (A), a commercially available product may be used. For example, “Epol” manufactured by Idemitsu Kosan Co., Ltd., “GI-2000”, “GI-3000”, “G-3000” manufactured by Nippon Soda Co., Ltd., etc. Examples thereof include “KRASOL HLBH P3000”, “KRASOL LBH-P2000”, and the like.
  • the polyol (A) may be used in combination of two or more depending on the purpose.
  • the aliphatic alcohol (B) having three or more hydroxyl groups is not particularly limited as long as it is an aliphatic alcohol having a molecular weight of 100 or more and less than 800.
  • a molecular weight of 800 or more is not preferable because the compatibility with the polyol (A) is deteriorated.
  • Specific examples include trimethylolpropane, pentaerythritol, glycerin, and modified compounds thereof.
  • the modifying compound include PPG-modified pentaerythritol and PPG-modified glycerin.
  • the resulting urethane (meth) acrylate (A) since the alcohol (B) has a plurality of (three or more) hydroxyl groups, the resulting urethane (meth) acrylate (A) has a branched structure, resulting in an increase in crosslink density. According to such urethane (meth) acrylate, it becomes possible to lower the (meth) acryloyl group concentration in urethane (meth) acrylate, which adversely affects the weather resistance and heat resistance of the cured product. It is possible to maintain the hardness.
  • the amount of alcohol (B) used is not particularly limited, but is, for example, 0.01 to 3% by weight with respect to the total amount of urethane (meth) acrylate-containing product obtained (100% by weight), preferably 0. It is 1 to 1% by weight, and more preferably 0.3 to 0.6% by weight.
  • it is less than 0.01% by weight, the heat resistance after heating of the cured product containing urethane (meth) acrylate to be obtained (see change in coating film hardness) is deteriorated.
  • it exceeds 3% by weight the molecular weight becomes too large during synthesis, which may cause gelation.
  • alcohol (B) Commercially available products may be used as the alcohol (B).
  • TMP Trimethylolpropane
  • Sanix HD-250 polypropylene glycol modified product of glycerin
  • 2 or more types of alcohol (B) may be used together according to the purpose.
  • the diisocyanate (C) include at least one selected from the group consisting of alicyclic diisocyanates, linear or branched aliphatic diisocyanates, and diisocyanate compounds obtained by hydrogenating aromatic isocyanates. . Although it does not restrict
  • the aliphatic diisocyanate is not particularly limited.
  • a linear aliphatic diisocyanate such as hexamethylene diisocyanate
  • a branched chain such as 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
  • chain aliphatic diisocyanates Although it does not restrict
  • diisocyanate (C) Commercially available products may be used as the diisocyanate (C).
  • VESTANAT IPDI isophorone diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate
  • HDI Hexamethylene diisocyanate
  • Diisocyanate (C) may be used in combination of two or more depending on the purpose.
  • the hydroxyl group-containing (meth) acrylate (D) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxynormalpropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.
  • a (meth) acrylate having two (meth) acryloyl groups, further having two or more (meth) acryloyl groups such as (meth) acrylate having a hydroxyl group and pentaacrylitol triacrylate, and further having a hydroxyl group.
  • (meth) acrylate (D) may use 2 or more types together according to the objective.
  • Alcohol (E) having one hydroxyl group examples include aliphatic or alicyclic primary alcohols having 3 or more carbon atoms, and the molecular weight thereof is preferably in the range of 70 to 400.
  • the alcohol has less than 3 carbon atoms or a molecular weight of less than 70, it is not preferred because it may volatilize during the synthesis of urethane (meth) acrylate.
  • the molecular weight exceeds 400, the reactivity with the isocyanate group is lowered, and the synthesis time may be prolonged, which is not preferable.
  • the alcohol which has an aromatic ring is unpreferable since the hue of the urethane (meth) acrylate (X) obtained may become high, or a weather resistance may be inferior.
  • Two or more alcohols may be used in combination depending on the purpose.
  • alcohol (E) examples include 1-butanol, 1-heptanol, 1-hexanol, normal octyl alcohol, 2-ethylhexyl alcohol, cyclohexane methanol, capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol (cetanol). , Stearyl alcohol and mixtures thereof. Of these, 2-ethylhexyl alcohol is preferred from the viewpoints of boiling point, price, and availability.
  • the active energy ray-curable composition of the present invention can accurately adjust the viscosity and adjust the Tg of the cured coating film when producing urethane (meth) acrylate.
  • the effect of preventing the increase in viscosity, the appearance of the resin, the suppression of by-products, the transparency of the cured product, the heat resistance and the like is achieved.
  • Monofunctional (meth) acrylate refers to (monofunctional) (meth) acrylate having one acryloyl group in the molecule.
  • (meth) acrylate (Y) may be used as a compatibilizing agent when forming the urethane isocyanate prepolymer.
  • raw materials for example, polyol (A), alcohol (B), diisocyanate (C), etc.
  • the viscosity of the reaction solution may increase. At this time, it also acts as a so-called diluent that alleviates the increase in viscosity.
  • the use concentration of (meth) acrylate (Y) is not particularly limited, but is, for example, 20 to 60% by weight, preferably 20% with respect to the total amount of urethane (meth) acrylate-containing product (100% by weight) obtained. ⁇ 40% by weight. If it is less than 20% by weight, the viscosity of the urethane (meth) acrylate obtained is increased, handling becomes difficult, and gelation may occur. On the other hand, when it exceeds 60% by weight, when applied, the viscosity is too low and the wettability with the transparent substrate is deteriorated, which may reduce the flexibility and heat resistance of the urethane (meth) acrylate.
  • Such (meth) acrylate (Y) is not particularly limited, but is preferably a monofunctional (meth) acrylate that is not a polyether acrylate (PO-modified product, EO-modified product, etc.) from the viewpoint of heat resistance, Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, ⁇ -carboxyethyl (Meth) acrylate, isobornyl (meth) acrylate, octyl / decyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, is
  • the (meth) acrylate (Y) may be a commercially available product.
  • the product name “ ⁇ -CEA” manufactured by Daicel Ornex Co., Ltd., ⁇ -carboxyethyl acrylate
  • the product name “IBOA” Disicel Ornex, isobornyl acrylate
  • product name "ODA-N” Disicel Ornex, octyl / decyl acrylate
  • product name "NOA” manufactured by Osaka Organic Chemicals, compound name: normal octyl acrylate
  • (meth) acrylate (Y) may use 2 or more types together according to the objective.
  • the photopolymerization initiator (Z) of the present invention varies depending on the type of active energy ray and the type of urethane (meth) acrylate (X), and is not particularly limited, but is a known photoradical polymerization initiator or photocationic polymerization initiation.
  • the amount of the photopolymerization initiator used is not particularly limited, but is, for example, 1 to 20 parts by weight, preferably 1 to 5 parts by weight with respect to 100 parts by weight of the active energy ray-curable composition. If the amount is less than 1 part by weight, there is a risk of causing poor curing. Conversely, if the amount of the photopolymerization initiator used is large, an odor derived from the photopolymerization initiator may remain from the cured coating film.
  • 2 or more types of photoinitiators (Z) may be used together according to the objective.
  • the active energy ray-curable composition of the present invention can be variously used as necessary.
  • Additives can be blended. Examples of such additives include fillers, dyes and pigments, leveling agents, ultraviolet absorbers, light stabilizers, antifoaming agents, dispersants, and thixotropic agents.
  • the addition amount of these additives is not particularly limited, but is, for example, 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the active energy ray-curable composition.
  • the laminate of the present invention comprises a cured product layer of the active energy ray-curable composition between a first transparent substrate selected from glass and plastic and a second transparent substrate selected from glass and plastic.
  • the active energy ray-curable composition is applied onto the first transparent substrate to form a resin layer, and the second transparent substrate is adhered onto the resin layer.
  • an active energy ray such as an ultraviolet ray or an electron beam
  • the active energy ray-curable composition is cured in a very short time to form a cured product layer to obtain a laminate.
  • FIG. 1 shows an embodiment of the laminate.
  • plastic base materials such as a transparent plastic film other than glass base materials, such as a transparent glass plate, can be used.
  • An existing transparent material can be used as the plastic substrate, and is not particularly limited.
  • polyolefin resin such as polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyethylene terephthalate
  • polyester resins such as polyethylene naphthalate and polybutylene terephthalate, acrylic resins, and polycarbonate resins.
  • polycarbonate resin and acrylic resin are particularly preferably used.
  • the application method is not particularly limited and spraying is performed.
  • a method, an airless spray method, an air spray method, a roll coat method, a bar coat method, a gravure method, or the like can be used.
  • the roll coat method is most preferably used from the viewpoints of aesthetics, cost, workability, and the like.
  • the application may be a so-called in-line coating method performed during the manufacturing process of a plastic film or the like, or a so-called off-line coating method in which coating is performed in a separate process on an already manufactured transparent substrate. From the viewpoint of production efficiency, off-line coating is preferred. In addition, it is preferable to use a cartridge in order to prevent bubbles from being generated.
  • the thickness of the coating film of the present invention is preferably 50 to 300 ⁇ m, more preferably 50 to 200 ⁇ m.
  • the layer thickness exceeds 300 ⁇ m, the amount of the resin composition to be applied becomes large, so that the cost may increase or the uniformity of the film thickness may decrease.
  • it is less than 50 micrometers the softness
  • the light source for performing ultraviolet irradiation is not particularly limited, and for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like is used.
  • the irradiation time varies depending on the type of the light source, the distance between the light source and the coating surface, and other conditions, but is several tens of seconds at most, and usually several seconds.
  • an irradiation source with a lamp output of about 80 to 300 W / cm is used.
  • the physical property measurement method, test method, and evaluation method are shown below.
  • Weight average molecular weight The weight average molecular weight was determined by GPC (gel permeation gas chromatography) method based on standard polystyrene under the following measurement conditions.
  • the transmittance was measured using only a micro glass as a reference, and evaluated according to the following criteria.
  • a glass laminate (test piece A) shown in FIG. 3 was prepared as follows. First, 0.200 g of the active energy ray-curable composition was accurately weighed on the center of a glass plate (thickness 1 mm, 5 cm square). Furthermore, the glass plate of the same shape was covered from the top, the resin layer was extended circularly (4 cm diameter), and the glass laminated body was obtained. Thereafter, a glass laminate (test piece A) having a cured resin composition layer is irradiated from the glass surface of one side of the glass laminate using a high-pressure mercury lamp (made by Eye Graphics Co., Ltd.) under the following conditions. Got.
  • a high-pressure mercury lamp made by Eye Graphics Co., Ltd.
  • test plate (Storage under heat-resistant conditions) Using a small environmental tester (product name SH-641, manufactured by Espec Corp.), the test plate (glass laminate, after curing) was stored at a temperature of 95 ° C. for 1000 hours.
  • APHA is measured using a spectroscopic color meter (product name: Spectro Color Meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.) by measuring APHA of the glass laminate before and after storage under heat-resistant conditions, and evaluated according to the following criteria: did.
  • a spectroscopic color meter product name: Spectro Color Meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.
  • a hardness was measured according to JIS K 6253.
  • the load at the time of measurement was 500 g, and the load drop rate was 9 mm / s.
  • the test piece B was stored for 1000 hours at a temperature of 95 ° C. If the numerical value of hardness before and after storage was less than ⁇ 20%, “ ⁇ ” was entered in the column “Change in coating film hardness” of “Heat resistance”. On the other hand, when the numerical value of the coating film hardness is ⁇ 20% or more, “x” is described.
  • the “value of hardness” can be calculated by dividing the hardness of the test piece B after storage by the hardness of the test piece B before storage.
  • the isocyanate group concentration was measured as follows. In addition, the measurement was performed under stirring with a stirrer in a 100 mL glass flask.
  • TMP trimethylolpropane, trifunctional alcohol, molecular weight: 134, white solid
  • product name “trimethylolpropane (TMP)” (manufactured by Mitsubishi Gas Chemical Company) “HD-402” (Compound name: PPG-modified pentaerythritol, trifunctional alcohol, hydroxyl value: 561 mg KOH / g, molecular weight: 400); product name: “Sanix HD-402” (manufactured by Mitsubishi Gas Chemical) “GP-250” (compound name: PPG-modified glycerin, trifunctional alcohol, hydroxyl value: 672 mg KOH / g, molecular weight: 250); product name “Sanniks GP-250” (manufactured by Mitsubishi Gas Chemical Company) “PCL308” (compound name: polycaprolactone-modified alcohol, trifunctional alcohol, hydroxyl value: 193 mg KOH / g, molecular
  • IPDI compound name isophorone diisocyanate
  • VESTANAT IPDI manufactured by Evonik
  • HDI compound name: hexamethylene diisocyanate
  • HDI manufactured by Nippon Polyurethane Co., Ltd.
  • TMDI compound name 2,2,4-trimethylhexamethylene diisocyanate
  • TMDI manufactured by Evonik
  • the completion of the reaction is that the isocyanate group concentration in the reaction solution is equal to or less than the residual isocyanate group concentration (hereinafter referred to as “theoretical end-point isocyanate group concentration”) when all of the hydroxyl groups subjected to the reaction are urethanized. That was confirmed.
  • the molar ratio of HLBH-P3000, TMP, IPDI, HEA, 2-EH used in the above reaction was 4.0: 0.6: 5.9: 1.02: 1.0.
  • Example 3 / X-3> Synthesis except that 262.6 g of GI-2000 was used as the polyol (A), 33.1 g of IPDI as the diisocyanate (C), and 129.3 g of NOA (30% by weight) as the (meth) acrylate (Y).
  • the molar ratio of GI2000, TMP, IPDI, HEA and 2-EH used in the above reaction was 6.0: 0.6: 7.9: 1.02: 1.0.
  • the active energy ray-curable composition containing the urethane (meth) acrylate (X) of the present invention has a good appearance of the resin before curing, and is filled with air between the films. Light scattering at the film interface can be prevented. Further, it was found that the cured product has the performance that the hue change, shape change, and coating film hardness do not change even when subjected to high heat for a long time.
  • Comparative Example 1 the active energy ray-curable composition in the case of not using alcohol (B) showed a large change in coating film hardness in the heat resistance (tablet) test. Further, as shown in Comparative Example 2, when the (meth) acryloyl group concentration in the urethane (meth) acrylate is 0.2 mol / kg, the change in the coating film hardness increases in the heat resistance (tablet) test due to curing shrinkage. It was. Furthermore, as shown in Comparative Example 3, when PCL308 was used as the alcohol (B), the compatibility with other components deteriorated, resulting in white turbidity, which could not be used as an active energy ray-curable composition. . As shown in Comparative Examples 4 and 5, when polypropylene glycol having excellent transparency was used as the polyol, it was found that the cured product had a drawback of liquefaction in the heat resistance test.
  • the active energy ray-curable composition of the present invention is not intended to increase the viscosity during the production of the urethane (meth) acrylate (X), which is a component, and the by-product of the by-product is small, and is intended. Urethane (meth) acrylate (X) can be produced.
  • the active energy ray-curable composition (before curing) of the present invention does not deteriorate the appearance of the resin due to white turbidity at low temperatures.
  • the active energy ray-curable composition of the present invention has good wettability with a glass substrate or a plastic substrate, high flexibility, high heat resistance, and low cure shrinkage, so that it is a smartphone or tablet.
  • the active energy ray curable composition of this invention can be used as an interlayer filler.
  • cured material and a base material is favorable.
  • the cured product of the active energy ray-curable composition of the present invention has high transparency and is less likely to be deformed or deteriorated in hue even at high temperatures.
  • the active energy ray-curable composition of the present invention is filled between transparent substrates of displays used in personal computers, car navigation systems, televisions, mobile phones (smartphones), tablets, etc. It is useful in that it can prevent light scattering in the layer and can obtain a laminate that hardly undergoes a hue change or a shape change during a heat resistance test.

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