WO2016117045A1 - Pressure-sensitive adhesive sheet, process for producing same, and process for producing optical member using same - Google Patents
Pressure-sensitive adhesive sheet, process for producing same, and process for producing optical member using same Download PDFInfo
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- WO2016117045A1 WO2016117045A1 PCT/JP2015/051468 JP2015051468W WO2016117045A1 WO 2016117045 A1 WO2016117045 A1 WO 2016117045A1 JP 2015051468 W JP2015051468 W JP 2015051468W WO 2016117045 A1 WO2016117045 A1 WO 2016117045A1
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- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- meth
- adhesive sheet
- acrylate
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Classifications
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- 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
- 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
-
- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
Definitions
- the present invention relates to a pressure-sensitive adhesive sheet, a method of producing the same, and a method of producing an optical member using the same. More specifically, for example, each component in the manufacture of optical members such as a liquid crystal cell of liquid crystal display device and a polarizing plate or a phase difference plate, a design panel of a touch panel and a touch sensor, and a touch panel and a liquid crystal module.
- the present invention relates to a pressure sensitive adhesive sheet useful for pasting.
- Liquid crystal display devices provided with a liquid crystal display are used not only as personal computers and televisions but also as display devices for various electronic devices such as smart phones, mobile phones, electronic organizers, car navigation systems and the like.
- a touch panel liquid crystal display device for inputting by touching a display screen has become widespread.
- liquid crystal display devices provided with a decorative printing step for decoration are increasing.
- a member provided with a frame-like printing step may be used as a member which constitutes a display portion of a smartphone.
- the pressure-sensitive adhesive sheet is required to have a performance capable of sufficiently filling the steps (that is, step absorbability).
- the step absorbability is improved by thickening the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet.
- it is not sufficient to thicken the pressure-sensitive adhesive layer.
- thickening the adhesive layer is contrary to the demand for downsizing and thinning of the product.
- the step absorbability is improved to some extent also by lowering the elastic modulus of the pressure-sensitive adhesive layer.
- a pressure-sensitive adhesive having a low elastic modulus has poor cohesion at high temperatures and thus has poor durability. For example, when a high-temperature or high-humidity heat accelerated test is performed, floating and peeling tend to occur in the periphery of the step. Further, along with this, the blister resistance required for a general touch panel adhesive also decreases.
- Patent Document 1 discloses a pressure-sensitive adhesive sheet having an acrylic pressure-sensitive adhesive layer exhibiting a specific storage elastic modulus and a specific peel adhesion, and the pressure-sensitive adhesive layer has an acrylic monomer having a crosslinkable functional group (component B) is used. And even if this adhesive sheet is a thin film, it is said that it is excellent in level difference absorbability and endurance.
- the thickness of the pressure-sensitive adhesive layer in the embodiment is relatively thin at 25 ⁇ m, and only the effect of following the 8 ⁇ m step can be obtained. That is, the effect on the larger step in recent years is insufficient.
- Patent Document 2 discloses a pressure-sensitive adhesive layer containing a cross-linked product of a functional group-containing acrylic resin produced by solution polymerization and a cross-linking agent, and an ethylenically unsaturated compound containing one ethylenically unsaturated group. A sheet is disclosed. And this pressure-sensitive adhesive sheet exhibits a high level of step followability, and is considered to be excellent in adhesion physical properties (adhesive strength, holding power), moisture heat resistance, and blister resistance.
- the acrylic pressure-sensitive adhesive containing a large number of hydroxyl groups is crosslinked with an isocyanate-based crosslinking agent, the end point of the crosslinking reaction can not be known, and even after the aging step, the characteristics change with time. This is a cause of peeling over time after bonding.
- Patent Document 3 is composed of an acrylic copolymer obtained by polymerizing a (meth) acrylic acid ester monomer, a (meth) acrylic acid ester monomer having a UV crosslinkable site of a benzophenone structure, and a hydrophilic monomer in a solvent.
- An adhesive sheet is disclosed. Then, the pressure-sensitive adhesive sheet is made to follow the level difference by heating and pressing, and the ultraviolet ray crosslinkable site is crosslinked by ultraviolet irradiation, and it is said that excellent level difference absorbability is exhibited by curing.
- the benzophenone structure is not excited by UV-A, and UV-B and UV-C are required.
- Patent Document 3 describes that diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO) may be contained.
- TPO diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
- the pressure-sensitive adhesive sheet becomes yellowish.
- TPO is excited even by visible light, there is a risk that a crosslinking reaction may be initiated by ordinary illumination at the time of processing of an adhesive sheet or at the time of panel production, and environmental control at the time of storage or work becomes complicated.
- the monomer having a benzophenone structure and the photoinitiator TPO are expensive, leading to an increase in the cost of the pressure-sensitive adhesive sheet.
- Patent Document 4 contains a (meth) acrylic polymer obtained by polymerizing a monomer component containing 30 to 90% by mass of an alkyl (meth) acrylate having an alkyl group having 10 to 22 carbon atoms at the ester end. And a radiation-curable pressure-sensitive adhesive characterized by having a radically polymerizable functional group having a carbon-carbon double bond. And this adhesive is considered to be excellent in step absorbability.
- the adhesive is synthesized in a solvent, coated with a solution and dried in the same manner as in Patent Document 2, and the acrylic adhesive containing a large number of hydroxyl groups is crosslinked with an isocyanate crosslinking agent. Problems of foaming and stability over time occur.
- step absorbability is insufficient in sheeted adhesive tape
- a thermosetting or ultraviolet curable liquid resin is poured between a member provided with a print layer and a member to be bonded thereto, heating or ultraviolet light
- thermosetting or ultraviolet curable liquid resin is poured between a member provided with a print layer and a member to be bonded thereto, heating or ultraviolet light
- a method of fixing the members by curing the resin by irradiation is effective for members having steps.
- an expensive apparatus for applying a fixed amount of liquid resin is required, and depending on the flow of the liquid, air bubbles between the members can not be completely removed, air bubbles are accumulated near the step, and heat or ultraviolet irradiation in the curing process is not sufficient. If it is sufficient, curing may be insufficient to cause air bubbles.
- the liquid resin has poor handleability.
- Patent Document 5 discloses a technique for imparting stress relaxation property by appropriately softening the adhesive layer by adding a plasticizer or the like to the adhesive.
- a plasticizer or the like added to the adhesive.
- the addition of the plasticizer causes the blister to contaminate the adherend when the polarizing plate is peeled off. Furthermore, since the cohesion is reduced, floating and peeling over time easily occur.
- the present invention has been made to solve the problems of the prior art described above. That is, the object of the present invention is to be excellent in the step absorptivity, the transparency, the blister resistance, the resistance to moisture and heat whitening, the high adhesiveness, the stability over time, etc. required of the optical member after curing. It is an object of the present invention to provide a pressure-sensitive adhesive sheet excellent in reworkability even when positional deviation or the like occurs, a method for producing the same, and a method for producing an optical member using the same.
- the present inventors do not use any solvent, and partially adhere to the non-reacted substance of the (meth) acrylate compound which is the main component of the pressure-sensitive adhesive layer. It has been found that the method of completely adhering by remaining in the agent layer and reacting the remaining unreacted material during the production of the optical member is very effective, and the present invention has been completed.
- the present invention is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer contains 50 to 85% by mass of (meth) acrylic acid ester (A) having only one unsaturated double bond in the molecule
- a syrupy acrylic resin composition obtained by partially polymerizing a monomer composition containing 15 to 50% by mass of a hydroxyl group-containing (meth) acrylic acid ester (B) having only one unsaturated double bond therein by a bulk polymerization method
- the present invention relates to a method for producing a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer, which comprises 50 to 85% by mass of (meth) acrylic acid ester (A) having only one unsaturated double bond in the molecule and in the molecule.
- a syrupy acrylic resin composition obtained by partially polymerizing a monomer composition containing 15 to 50% by mass of a hydroxyl group-containing (meth) acrylic acid ester (B) having only one unsaturated double bond by a bulk polymerization method, A step (1) of preparing a solventless curable resin composition containing a multifunctional (meth) acrylate compound (C) and a photopolymerization initiator, and an active energy ray of the solventless curable resin composition. It is a manufacturing method of the adhesive sheet which has the process (2) of hardening
- the present invention is a method for producing an optical member including a component adhered using a pressure-sensitive adhesive sheet, which comprises bonding an adherend using the pressure-sensitive adhesive sheet of the present invention (3), and the adherend
- the adhesive layer of the pressure-sensitive adhesive sheet after laminating is irradiated with active energy rays to polymerize the unreacted (meth) acrylate compounds (A) and (B) remaining in the pressure-sensitive adhesive layer for complete adhesion
- a manufacturing method of an optical member which has a process (4).
- the pressure-sensitive adhesive sheet of the present invention is excellent in step absorbability, and also excellent in reworkability after bonding. Moreover, according to the method for producing an optical member of the present invention, it is possible to provide an optical member excellent in properties such as transparency, blister resistance, wet heat whitening resistance, high adhesiveness, and temporal stability.
- the monomer composition used in the present invention contains at least (meth) acrylic acid ester (A) and hydroxyl group-containing (meth) acrylic acid ester (B).
- (Meth) acrylic acid ester is a generic term for acrylic acid ester and methacrylic acid ester.
- (Meth) acrylic acid ester (A) is a (meth) acrylic acid ester having only one unsaturated double bond in the molecule (however, components (B) and (C), ie, hydroxyl group-containing (meth) (Except for acrylic ester and multifunctional (meth) acrylate compound).
- the (meth) acrylic acid ester (A) is desirably a compound which does not contain a crosslinkable functional group (a crosslinkable functional group other than the above-mentioned unsaturated double bond).
- aliphatic (meth) acrylic acid esters are preferable, and in particular, 2-ethylhexyl (meth) acrylate and / or butyl (meth) acrylate is more preferably used as a main monomer.
- the hydroxyl group-containing (meth) acrylic acid ester (B) is a (meth) acrylic acid ester having only one unsaturated double bond in the molecule and having one or more hydroxyl groups.
- the hydroxyl group-containing (meth) acrylic acid ester (B) is also preferably a compound which does not contain a crosslinkable functional group (the above-mentioned unsaturated double bond and a crosslinkable functional group other than the hydroxyl group).
- aliphatic (meth) acrylates containing a hydroxyl group are preferable, and 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, in particular More preferred are 2-hydroxybutyl methacrylate and 6-hydroxyhexyl (meth) acrylate.
- the amount of (meth) acrylic acid ester (A) in the monomer composition is 50 to 85% by mass, preferably 65 to 80% by mass.
- the amount of the hydroxyl group-containing (meth) acrylic acid ester (B) is 15 to 50% by mass, preferably 20 to 35% by mass.
- the monomer composition includes, in addition to the (meth) acrylic acid ester (A) and the hydroxyl group-containing (meth) acrylic acid ester (B) described above, other ethylenically unsaturated groups as long as the effects of the present invention are not impaired. It may contain an ethylenically unsaturated compound containing one of them.
- the syrupy acrylic resin composition used in the present invention is obtained by partially polymerizing the monomer composition by bulk polymerization.
- the bulk polymerization method is a method of polymerizing only monomers without using a solvent or water.
- a polymerization method such as solution polymerization, suspension polymerization or emulsion polymerization is performed, it is necessary to volatilize and remove the solvent or water after the polymerization in order to finally obtain a solvent-free curable resin composition.
- additional steps such as volatilization removal are unnecessary.
- the bulk polymerization is performed, for example, by adding a radical polymerization initiator to the monomer composition and photopolymerizing or thermally polymerizing under nitrogen.
- the photopolymerization is preferably performed by ultraviolet irradiation with the addition of a photopolymerization initiator.
- the thermal polymerization is preferably performed by heating at 50 to 200 ° C. with the addition of a thermal polymerization initiator. In general, it takes about 6 to 10 hours to react approximately 100% of the monomers, but in partial polymerization by bulk polymerization, it is sufficient if the monomers are partially polymerized, so approximately 2 hours is sufficient. .
- Partial polymerization is a method of stopping the reaction in the middle of the polymerization reaction without completely polymerizing the monomer composition.
- a syrupy acrylic resin composition in which the produced polymer is dissolved in unreacted monomers is obtained.
- the polymerization reaction is easily stopped by stopping light irradiation and exposing to air.
- the polymerization reaction is easily stopped by stopping heating, cooling and exposing to air.
- the addition of a polymerization terminator is also effective for terminating the reaction. However, it is preferable not to use a polymerization terminator because polymerization may be inhibited when performing the later polymerization.
- the monomer composition can be easily adjusted in viscosity by adjusting the conversion rate to polymer (polymer concentration).
- polymer concentration polymer concentration
- it is easy to obtain a viscosity suitable for coating on a substrate, and it is also useful in terms of productivity and energy saving.
- the solventless curable resin composition used in the present invention is a composition containing the syrupy acrylic resin composition described above, the multifunctional (meth) acrylate compound (C), and a photopolymerization initiator.
- This solventless curable resin composition is also preferably a syrupy composition.
- the polyfunctional (meth) acrylate compound (C) is a (meth) acrylate compound having two or more unsaturated double bonds in the molecule, and is a component for improving the cohesion of the pressure-sensitive adhesive layer by a crosslinking reaction. It is.
- Specific examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4- Bifunctional or higher polyvalent alkyl acrylate monomers such as butanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate; isocyanate group And urethane acrylate and epoxy acrylate which are oligomerized or polymerized by reacting acrylic acid and hydroxyl group-containing acrylate with a compound having a plurality of glycidyl groups.
- Two or more polyfunctional (meth) acrylate compounds (C) may be used in combination.
- 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol unit having 4 or 9 Preferred are polyethylene glycol di (meth) acrylates of
- the photoinitiator examples include acetophenone initiator, benzoin ether initiator, ketal initiator, phosphine oxide initiator, benzophenone initiator, benzoin initiator, halogenated ketone initiator, acyl Phosphate initiators can be mentioned.
- acetophenone-based initiators are preferred from the viewpoint of the color of the photoinitiator, yellowing resistance, and the ultraviolet ray region to be excited.
- an additional copolymerizable monomer may be added to adjust the viscosity and improve the properties of the cured product.
- the proportion of the polymer in the solventless curable resin composition is preferably 10 to 50% by mass, more preferably 20 to 40% by mass.
- the viscosity of the solvent-free curable resin composition is preferably 10,000 to 30,000 mPa ⁇ s, more preferably 15,000 to 25,000 mPa ⁇ s at 23 ° C.
- the weight average molecular weight of the polymer in the solvent-free curable resin composition is preferably 500,000 to 2000,000, more preferably 700, as determined by gel permeation chromatography (GPC) using polystyrene as a standard. It is from 000 to 1,500,000.
- the molecular weight can be adjusted, for example, by reaction temperature or addition of a chain transfer agent.
- the proportion of the polymer is adjusted when the viscosity is adjusted to about 20,000 mPa ⁇ s. Is about 20% by mass.
- the solvent-free curable resin composition may contain components other than the components described above, as long as the effects of the present invention are not impaired.
- the solventless curable resin composition preferably further contains a silane coupling agent.
- a silane coupling agent for example, a relatively large amount of hydroxyl group-containing (meth) acrylic acid ester (B) is added, it tends to contain water under high temperature and high humidity conditions. And, if it contains water, the adhesion will temporarily decrease, but if it is left from the high temperature and high humidity conditions and left in the normal state for about 72 hours, the water will be removed and the adhesion will recover.
- a copolymerized synthetic monomer having a high homopolymer Tg for example, a monomer having a Tg of 0 ° C.
- the Tg of the copolymer is increased, the step absorbability is reduced, or the adhesion is increased to reduce the reworkability.
- many copolysynthetic monomers having high Tg have a strong odor, and they tend to adversely affect the workability in the process of laminating the composition containing the monomers as in the present invention.
- silane coupling agent a silane coupling agent known in the field of pressure sensitive adhesive can be used. Specific examples thereof include mercapto group-containing silane coupling agents, epoxy group-containing silane coupling agents, amino group-containing silane coupling agents, and isocyanurate group-containing silane coupling agents.
- the content of the silane coupling agent is preferably 0.01 to 5 parts by mass, more preferably 0.2 to 1.0 parts by mass with respect to 100 parts by mass of the acrylic resin (component to be a resin after curing).
- the heat and whitening resistance, reworkability, and adhesion under high temperature and high humidity conditions are different due to the action different from the prior art. It will exert the effect of stabilizing the power.
- the solventless curable resin composition preferably further contains a chain transfer agent for molecular weight control after curing.
- a chain transfer agent for molecular weight control after curing.
- the chain transfer agent include n-dodecanethiol (lauryl mercaptan), glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, methyl thioglycolate, ethyl thioglycollate, 2-ethylhexyl thioglycollate, ⁇ Thioglycerol and 2,3-dimercapto-1-propanol are mentioned.
- Two or more chain transfer agents may be used in combination.
- the addition amount of the chain transfer agent is preferably 0.001 to 0.01 parts by mass in 100% by mass of the solvent-free curable resin composition, though it depends on the level of the target molecular weight.
- the solventless curable resin composition further contains a benzotriazole-based rust inhibitor.
- a benzotriazole-based rust inhibitor include benzotriazole described in JP-A-2013-166846 and derivatives thereof.
- a non-solvent type curable resin composition does not contain the component which has a carboxyl group from the point of metal corrosion.
- the pressure-sensitive adhesive layer is a layer formed by curing the solventless curable resin composition described above by irradiation with active energy rays.
- a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer can be obtained.
- the irradiation of active energy rays is preferably performed while preventing the influence of oxygen having a polymerization inhibiting function as much as possible.
- the irradiation method for example, a method of performing in a nitrogen gas atmosphere or in an inert gas atmosphere, polyethylene terephthalate which allows active energy rays to pass through to a solventless curable resin composition cast on a support but blocks oxygen Etc., there is a method of laminating films.
- the solventless UV curable resin composition cast on a support or a release film such as polyethylene terephthalate is further laminated with a release film such as polyethylene terephthalate and then irradiated. And curing is preferred.
- the present invention is one of the important features that the unreacted (meth) acrylate compounds (A) and (B) partially remain in the pressure-sensitive adhesive layer. Specifically, this feature is in the point of a so-called semi-cured state in which unsaturated double bonds remain in the pressure-sensitive adhesive layer.
- FT-IR Fourier transform IR spectrum
- the amount of the monomer remaining in the pressure-sensitive adhesive sheet varies depending on the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet and the level difference to be absorbed, but preferably about 5 to 20% by mass.
- the amount of the remaining monomer is 20% by mass or less, it is relatively easy to maintain the thickness of the pressure-sensitive adhesive layer, the decrease in punching processability is suppressed, and good workability can be maintained.
- it is 5 mass% or more, favorable level difference absorbency will express.
- the active energy ray for example, light rays such as ultraviolet rays, far ultraviolet rays, near ultraviolet rays and infrared rays, electromagnetic waves such as X rays and ⁇ rays, electron rays, proton rays and neutron rays can be used.
- UV irradiation is preferred in view of curing speed, availability of the irradiation apparatus, cost and the like.
- a light source for example, a high pressure mercury lamp, an electrodeless lamp, an ultra high pressure mercury lamp, a metal halide lamp, a chemical lamp, and a fluorescent UV lamp can be mentioned.
- those that emit relatively weak ultraviolet light such as black light and fluorescent UV lamps are easier to adjust the semi-cured state than those that emit high-intensity ultraviolet light such as electrodeless lamps and high-pressure mercury lamps .
- the irradiation time depends on the thickness of the pressure-sensitive adhesive layer, but the black light exhibits excellent step absorbability for about 30 to 90 seconds.
- the irradiation time is shorter than 30 seconds, the cohesive strength of the pressure-sensitive adhesive layer is insufficient, the release film can not be peeled off, the pressure-sensitive adhesive may stick out, and the punchability in a predetermined shape is extremely deteriorated.
- the irradiation time is longer than 60 seconds, the remaining unsaturated double bonds are extremely reduced, and the step absorbability deteriorates.
- the pressure-sensitive adhesive sheet of the present invention is obtained by forming the pressure-sensitive adhesive layer as described above.
- the pressure-sensitive adhesive sheet usually has a substrate, and a pressure-sensitive adhesive layer is formed on one side or both sides of the substrate.
- a pressure-sensitive adhesive sheet having a substrate a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on both sides of the substrate is particularly preferable.
- the substrate is not particularly limited, and a known substrate may be used. Specific examples thereof include polyethylene terephthalate (PET) films, polybutylene terephthalate films, polyethylene naphthalates, and olefin films.
- PET polyethylene terephthalate
- the thickness of the substrate is preferably 12 to 180 ⁇ m, more preferably 50 to 125 ⁇ m
- the thickness of the pressure-sensitive adhesive layer is preferably 5 to 500 ⁇ m, more preferably 25 to 300 ⁇ m
- the thickness of the pressure-sensitive adhesive sheet Is preferably 30 to 1000 ⁇ m, more preferably 125 to 550 ⁇ m.
- the adherends are bonded using the pressure-sensitive adhesive sheet according to the present invention described above (preferably, pressure is applied through the pressure-sensitive adhesive sheet or pressure is applied to heat the adherends Bonding), the non-reacted (meth) acrylate compounds (A) and (B) remaining in the pressure-sensitive adhesive layer are polymerized by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet after bonding with an active energy ray. Completely adhere.
- the present invention is very useful when at least one of the adherends is a transparent part.
- heat and pressure treatment is performed in an autoclave at a temperature of 23 to 60 ° C. and a pressure of 0.3 to 0.5 MPa for 30 to 60 minutes.
- the method is preferred.
- an active energy ray after bonding a to-be-adhered body and an adhesive sheet it irradiates from a base material sheet or a transparent to-be-adhered surface.
- the type of active energy ray and the light source are the same as those described above.
- the amount of ultraviolet radiation to be irradiated is about 300 to 3000 mJ / cm 2 .
- the adherend is not particularly limited, but, for example, an ITO electrode film, a transparent electrode film such as an organic conductive film such as polythiophene, a polarizing plate, a retardation plate, an elliptically polarizing plate, an optical compensation film, a brightness enhancement film, an electromagnetic wave shielding film And optical components such as near-infrared absorbing film, AR (antireflection) film, etc., and glass subjected to each treatment.
- adherends that can transmit active energy rays are preferable.
- the pressure-sensitive adhesive sheet excellent in the step following property of the present invention for an adherend having a step of 3 to 100 ⁇ m by decorative printing or the like.
- bonding of optical members having a step bonding of optical members without a step (such as touch panel and image display module), particularly bonding of hard members is also possible. They are useful in that they are efficiently bonded with a pressure-sensitive adhesive sheet thinner than conventional optical pressure-sensitive adhesive sheets.
- Example 1 Preparation of solvent-free curable resin composition
- 0.05 parts of 1,6-hexanediol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester A-HD-N
- a crosslinking agent 100 parts of the syrupy acrylic resin composition a
- additional photopolymerization 0.5 parts of acetophenone type initiator (manufactured by BASF Japan Ltd., trade name Darocure 1173) and 0.5 parts of benzotriazole (trade name BTZ-M manufactured by Kyodo Pharmaceutical Co., Ltd.) were added and uniformly stirred. .
- the air bubbles mixed at the time of stirring were removed by a degassing operation to obtain a solventless curable resin composition.
- the above solventless curable resin composition was coated on a 50 ⁇ m thick polyethylene terephthalate (PET) film treated with a release agent. It was covered with a 50 ⁇ m-thick release-agent-treated PET film and irradiated with ultraviolet light for 40 seconds with a black light to obtain a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer (0.1 mm thickness).
- the amount of residual monomer in the pressure-sensitive adhesive layer is shown in Table 2.
- the amount of the remaining monomer is the mass of the monomer volatilized by weighing the non-solvent curable resin composition sheeted into a sheet on an aluminum tray and heating it at 150 ° C. for 2 hours using a hot plate or the like.
- Example 2 A solvent-free curable resin composition as in Example 1 except that 0.03 parts of n-dodecanethiol (nDSH) was further added as a chain transfer agent to 100 parts of the syrupy acrylic resin composition a. Were prepared to prepare a pressure-sensitive adhesive sheet.
- nDSH n-dodecanethiol
- Example 3 Furthermore, 0.03 parts of n-dodecanethiol (nDSH) as a chain transfer agent and an epoxy-based silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) are added to 100 parts of the syrupy acrylic resin composition a.
- nDSH n-dodecanethiol
- an epoxy-based silane coupling agent trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.
- Example 4 A non-solvent curable resin composition was prepared in the same manner as in Example 3 except that the syrupy acrylic resin composition b was used instead of the syrupy acrylic resin composition a, to prepare a pressure-sensitive adhesive sheet.
- Example 5 A solventless curable resin composition was prepared in the same manner as in Example 3 except that the syrupy acrylic resin composition c was used instead of the syrupy acrylic resin composition a, to prepare a pressure-sensitive adhesive sheet.
- Comparative Example 1 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 2 except that the irradiation time of the ultraviolet light was changed from 40 seconds to 120 seconds.
- Comparative Example 2 (corresponding to an example of Patent Document 2) (Preparation of pressure-sensitive adhesive composition) A 55% ethyl acetate solution of tolylene diisocyanate adduct of trimethylolpropane as a crosslinking agent (100 parts by solid content: 50% by mass) of a solvent type acrylic resin composition d (Coronate L-55E, manufactured by Nippon Polyurethane Co., Ltd.) 0.
- the pressure-sensitive adhesive composition solution was applied to a release agent-treated PET film so that the thickness after drying was 0.10 mm, and dried at 100 ° C. for 5 minutes to form a pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer was sandwiched by a release-agent-treated PET film and aged at 40 ° C. for 3 days to obtain a pressure-sensitive adhesive sheet.
- Comparative Example 3 (corresponding to an example of Patent Document 1) (Preparation of pressure-sensitive adhesive composition)
- solvent type acrylic resin e 1.4 parts of a polyfunctional isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HL) as a crosslinking agent was blended to obtain a pressure-sensitive adhesive composition solution.
- Coronate HL a polyfunctional isocyanate compound
- a pressure-sensitive adhesive sheet was produced in the same manner as in Comparative Example 2 except that the pressure-sensitive adhesive composition solution was used.
- ITO resistance to conductive deterioration A substrateless adhesive sheet is bonded to an ITO-deposited PET film (trade name: 300RK, manufactured by Toyobo Co., Ltd.) coated with Ag paste as an electrode portion, and a sample obtained by bonding a PET film to the opposite side is 800 mJ with a high pressure mercury lamp It was irradiated with ultraviolet rays / mm 2 and cured. Then, it is left to stand in a 65 ° C., 90% RH atmosphere for 500 hours, the resistance value before and after promotion is measured with a multimeter, using an ITO film not attached with an adhesive sheet as a blank. A percentage (%) was given as a pass ( ⁇ ), and more than this was given as a rejection ( ⁇ ).
- a pressure-sensitive adhesive sheet was attached to a glass plate, and PET # 125 was attached to the opposite side to prepare a laminated sample.
- the laminated sample was irradiated with ultraviolet light of 800 mJ / mm 2 with a high pressure mercury lamp to be cured. Then, it was left to stand in an atmosphere of 85 ° C. and 85% RH for 250 hours, and it was visually confirmed that there was no foaming or floating of the laminated portion. Those with no float and no bubble were regarded as pass ( ⁇ ), and those with float or bubble were regarded as fail ( ⁇ ).
- Step absorbability Place a L-shaped film cut out with a width of 10 mm in a predetermined thickness as a step on a glass plate, and stick it on the glass plate with a pressure-sensitive adhesive sheet (40 mm x 50 mm) to sandwich the step.
- the laminated sample was produced by sticking # 125.
- the laminated sample was heated and pressurized in an autoclave at 60 ° C., 0.5 MPa ⁇ 30 minutes, and irradiated with ultraviolet light of 800 mJ / mm 2 with a high pressure mercury lamp to be cured.
- the cured laminate was allowed to stand in an atmosphere of 85 ° C. and 85% RH for 250 hours, and visually confirmed that there were no floating or bubbles around the step. Those with no float and no bubble were regarded as pass ( ⁇ ), and those with float or bubble were regarded as fail ( ⁇ ).
- a pressure-sensitive adhesive sheet (25 mm width) was attached to a glass plate, and PET # 125 was attached to the opposite side to prepare a laminated sample.
- the laminated sample was irradiated with ultraviolet light of 800 mJ / mm 2 with a high pressure mercury lamp to be cured. Two hours later, the PET film and the adhesive sheet were peeled off at a speed of 300 mm / min in the direction of 90 ° with respect to the glass plate with a tensile tester, and the adhesion at that time was measured.
- the cured laminated sample was left under an atmosphere of 85 ° C. and 85% RH for 250 hours, and 90 ° tack was measured 2 hours after taking out at room temperature.
- a pressure-sensitive adhesive sheet of 25 mm in width was attached to a glass plate, and PET # 125 was attached to the opposite side to prepare a laminated sample.
- the produced laminated sample was irradiated with ultraviolet light of 800 mJ / mm 2 with a high pressure mercury lamp to be cured. Thereafter, it was left for 72 hours in a 90 ° C. atmosphere, and after 2 hours of removal, the PET film and the adhesive sheet were peeled off at a speed of 300 mm / min in the 90 ° direction to the glass plate to confirm the presence or absence of adhesive residue on the glass plate .
- the pressure-sensitive adhesive sheets of Examples 1 to 5 are excellent in step absorptivity and reworkability, and also have the properties required as a pressure-sensitive adhesive for optical members, even in a high temperature and high humidity environment. Stable adhesion was obtained.
- Example 1 since the acrylic resin composition a was used, the transparency, the whitening resistance, the foam resistance and the reworkability were good. However, since it is a pressure-sensitive adhesive sheet in a state in which substantially no unreacted monomer remains in the pressure-sensitive adhesive layer (remaining monomer amount: 0.2%), the step absorbability is poor, and a 30 ⁇ m step can not be absorbed. . On the other hand, in Example 1 in which the same acrylic resin composition a is used, it is a pressure-sensitive adhesive sheet in a state in which unreacted monomers remain in the pressure-sensitive adhesive layer (remaining monomer amount: 14.3%). It was able to absorb 50 ⁇ m steps.
- Example 2 since the chain transfer agent was further added, a step of 75 ⁇ m could be absorbed, and other properties and reworkability were also good.
- Example 3 since the silane coupling agent was further added, the adhesion to glass after promotion of wet heat was also stable without lowering while the step absorbability and rework property were maintained.
- Comparative Example 2 since the solvent type acrylic resin composition d and isostearyl acrylate were used, the pressure-sensitive adhesive itself after ultraviolet irradiation became cloudy, and the transparency and the moisture-heat-heat whitening resistance were inferior. Moreover, since it was crosslinked with an isocyanate compound, the stability over time was poor, and foaming and floating occurred under high temperature and high humidity, and the step absorbability was also inferior.
- Comparative Example 3 since the solvent type acrylic resin composition e was used, the remaining solvent was volatilized when placed under high temperature and high humidity to cause foaming. In addition, since the monomers are almost completely polymerized at the time of solution polymerization, the step absorbability was also inferior. However, since almost no functional group-containing monomer was used for the adhesive, the tackiness was weak but the reworkability was good.
- the pressure-sensitive adhesive sheet of the present invention is excellent in step absorbability and reworkability. Furthermore, after curing, the optical member is also excellent in the properties required for the optical member such as transparency, blister resistance, moisture heat whitening resistance, high adhesion, and stability over time. Therefore, it is useful in the use which carries out adhesion fixation of the parts of various optical members in various products, such as a smart phone, a mobile phone, an electronic notebook, a car navigation system, a personal computer, a television, etc. In particular, it is more useful in the use which carries out adhesion fixation of parts which have level differences, such as a decoration printing level difference. Specific examples of particularly useful applications include bonding of liquid crystal cells of liquid crystal display devices with polarizing plates and retardation plates, bonding of design panels of touch panels with touch sensors, bonding of touch panels with liquid crystal modules, etc. The attachment of each part in manufacture is mentioned.
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Abstract
Description
本発明に用いるモノマー組成物は、少なくとも(メタ)アクリル酸エステル(A)と水酸基含有(メタ)アクリル酸エステル(B)を含む。「(メタ)アクリル酸エステル」は、アクリル酸エステルとメタクリル酸エステルの総称である。 <Monomer composition>
The monomer composition used in the present invention contains at least (meth) acrylic acid ester (A) and hydroxyl group-containing (meth) acrylic acid ester (B). "(Meth) acrylic acid ester" is a generic term for acrylic acid ester and methacrylic acid ester.
本発明に用いるシロップ状アクリル樹脂組成物は、モノマー組成物を塊状重合法により部分重合して得られる。 <Syrup-like acrylic resin composition>
The syrupy acrylic resin composition used in the present invention is obtained by partially polymerizing the monomer composition by bulk polymerization.
本発明に用いる無溶剤型硬化性樹脂組成物は、以上説明したシロップ状アクリル樹脂組成物と、多官能性(メタ)アクリレート化合物(C)と、光重合開始剤を含む組成物である。この無溶剤型硬化性樹脂組成物も、好ましくはシロップ状の組成物である。 <Solvent-free curable resin composition>
The solventless curable resin composition used in the present invention is a composition containing the syrupy acrylic resin composition described above, the multifunctional (meth) acrylate compound (C), and a photopolymerization initiator. This solventless curable resin composition is also preferably a syrupy composition.
なお、無溶剤型硬化性樹脂組成物は、金属腐食の点から、カルボキシル基を有する成分を含まないことが好ましい。 It is preferable that the solventless curable resin composition further contains a benzotriazole-based rust inhibitor. Specific examples thereof include benzotriazole described in JP-A-2013-166846 and derivatives thereof.
In addition, it is preferable that a non-solvent type curable resin composition does not contain the component which has a carboxyl group from the point of metal corrosion.
本発明において粘着剤層は、以上説明した無溶剤型硬化性樹脂組成物を活性エネルギー線の照射により硬化して形成した層である。例えば、無溶剤型硬化性樹脂組成物を剥離フィルム又は基材に塗布し、活性エネルギー線を照射することにより、粘着剤層を有する粘着シートが得られる。 <Pressure-sensitive adhesive layer>
In the present invention, the pressure-sensitive adhesive layer is a layer formed by curing the solventless curable resin composition described above by irradiation with active energy rays. For example, by applying a solventless curable resin composition to a release film or a substrate and irradiating an active energy ray, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer can be obtained.
以上のようにして粘着剤層を形成することにより、本発明の粘着シートが得られる。粘着シートは通常は基材を有し、その基材の片面又は両面に粘着剤層が形成される。基材を有する粘着シートの場合は、特に基材の両面に粘着剤層を有する両面粘着シートが好ましい。 <Adhesive sheet>
The pressure-sensitive adhesive sheet of the present invention is obtained by forming the pressure-sensitive adhesive layer as described above. The pressure-sensitive adhesive sheet usually has a substrate, and a pressure-sensitive adhesive layer is formed on one side or both sides of the substrate. In the case of a pressure-sensitive adhesive sheet having a substrate, a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on both sides of the substrate is particularly preferable.
本発明の光学部材の製造方法においては、以上説明した本発明の粘着シートを用いて被接着物を貼り合わせ(好ましくは粘着シートを介して加圧、又は加熱しながら加圧して被接着物を貼り合わせ)、貼り合わせた後の粘着シートの粘着剤層に活性エネルギー線を照射することにより、粘着剤層中に残存する未反応の(メタ)アクリレート化合物(A)及び(B)を重合させて完全接着する。特に本発明は、被接着物の少なくとも一方が透明な部品である場合に非常に有用である。 <Method of Manufacturing Optical Member>
In the method for producing an optical member according to the present invention, the adherends are bonded using the pressure-sensitive adhesive sheet according to the present invention described above (preferably, pressure is applied through the pressure-sensitive adhesive sheet or pressure is applied to heat the adherends Bonding), the non-reacted (meth) acrylate compounds (A) and (B) remaining in the pressure-sensitive adhesive layer are polymerized by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet after bonding with an active energy ray. Completely adhere. In particular, the present invention is very useful when at least one of the adherends is a transparent part.
攪拌機、還流冷却器、温度計、UVランプ及び窒素ガス導入口を備えた反応容器に、表1に示す組成(%)のアクリルモノマーを仕込み、さらにモノマー合計100部に対し、光重合開始剤としてアセトフェノン系開始剤(BASFジャパン社製、商品名ダロキュア1173)0.01部、連鎖移動剤としてn-ドデシルメルカプタン0.01部を添加した。そして窒素雰囲気下、UV光を照射することにより塊状重合法による部分重合を行い、無溶剤型シロップ状アクリル樹脂組成物a~cを得た。組成物中のポリマーの重量平均分子量(Mw)と濃度(%)を表1に示す。 <Preparation of Solvent-Free Syrup-Like Acrylic Resin Compositions a to c>
An acrylic monomer of the composition (%) shown in Table 1 is charged into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a UV lamp and a nitrogen gas inlet, and further 100 parts of the total monomer as a photopolymerization initiator 0.01 part of an acetophenone-based initiator (manufactured by BASF Japan, trade name: Darocure 1173) and 0.01 part of n-dodecyl mercaptan as a chain transfer agent were added. Then, UV irradiation was performed in a nitrogen atmosphere to carry out partial polymerization by bulk polymerization to obtain a solvent-free syrupy acrylic resin compositions a to c. The weight average molecular weight (Mw) and the concentration (%) of the polymer in the composition are shown in Table 1.
冷却管、撹拌機及び温度計を備えた反応容器に、表1に示す組成(%)のアクリルモノマーを仕込み、さらにモノマー合計100部に対して重合開始剤として2,2'-アゾビスイソブチロニトリル0.2部、溶媒として酢酸エチル100部を加えた。そして雰囲気下、68℃で4時間重合し、さらに追加の2,2'-アゾビスイソブチロニトリル0.2部を添加して80℃で2時間重合して、溶剤型アクリル樹脂組成物d~eを得た。組成物中のポリマーの重量平均分子量(Mw)と濃度(%)を表1に示す。 <Preparation of Solvent Type Acrylic Resin Composition d to e>
An acrylic monomer having the composition (%) shown in Table 1 is charged into a reaction vessel equipped with a cooling pipe, a stirrer and a thermometer, and 2,2'-azobisisobutyst as a polymerization initiator per 100 parts of the total of monomers. 0.2 parts of ronitrile and 100 parts of ethyl acetate as a solvent were added. Then, polymerization is carried out at 68 ° C. for 4 hours in an atmosphere, and 0.2 parts of additional 2,2′-azobisisobutyro nitrile is further added, followed by polymerization at 80 ° C. for 2 hours to obtain a solvent type acrylic resin composition d I got ~ e. The weight average molecular weight (Mw) and the concentration (%) of the polymer in the composition are shown in Table 1.
「2EHA」:アクリル酸2-エチルヘキシル
「HEA」:アクリル酸2-ヒドロキシエチル
「4HBA」:アクリル酸4-ヒドロキシブチル
「AME」:メトキシエチルアクリレート The abbreviations in Table 1 are as follows.
"2EHA": 2-ethylhexyl acrylate "HEA": 2-hydroxyethyl acrylate "4HBA": 4-hydroxybutyl acrylate "AME": methoxyethyl acrylate
(無溶剤型硬化性樹脂組成物の調製)
シロップ状アクリル樹脂組成物a100部に対して、架橋剤として1,6-ヘキサンジオールジアクリレート(新中村化学工業社製、商品名NKエステルA-HD-N)0.05部、追加の光重合開始剤としてアセトフェノン系開始剤(BASFジャパン社製、商品名ダロキュア1173)0.5部、ベンゾトリアゾ-ル(共同薬品社製、商品名BTZ-M)0.5部を添加して均一に撹拌した。撹拌時に混入した空気泡を脱泡操作により除去して、無溶剤型硬化性樹脂組成物を得た。 Example 1
(Preparation of solvent-free curable resin composition)
0.05 parts of 1,6-hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester A-HD-N) as a crosslinking agent to 100 parts of the syrupy acrylic resin composition a, and additional photopolymerization As an initiator, 0.5 parts of acetophenone type initiator (manufactured by BASF Japan Ltd., trade name Darocure 1173) and 0.5 parts of benzotriazole (trade name BTZ-M manufactured by Kyodo Pharmaceutical Co., Ltd.) were added and uniformly stirred. . The air bubbles mixed at the time of stirring were removed by a degassing operation to obtain a solventless curable resin composition.
上記無溶剤型硬化性樹脂組成物を、離型剤処理した厚さ50μmのポリエチレンテレフタレート(PET)フィルム上に塗工した。その上に厚さ50μmの離型剤処理したPETフィルムで被覆し、ブラックライトにより紫外線を40秒間照射して、粘着剤層(0.1mm厚)を有する粘着シートを得た。その粘着剤層中の残存モノマー量を表2に示す。残存モノマー量は、シート化させた無溶剤型硬化性樹脂組成物をアルミトレイに秤量し、ホットプレートなどを用いて150℃で2時間加熱し、揮発したモノマーの質量である。 (Production of adhesive sheet)
The above solventless curable resin composition was coated on a 50 μm thick polyethylene terephthalate (PET) film treated with a release agent. It was covered with a 50 μm-thick release-agent-treated PET film and irradiated with ultraviolet light for 40 seconds with a black light to obtain a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer (0.1 mm thickness). The amount of residual monomer in the pressure-sensitive adhesive layer is shown in Table 2. The amount of the remaining monomer is the mass of the monomer volatilized by weighing the non-solvent curable resin composition sheeted into a sheet on an aluminum tray and heating it at 150 ° C. for 2 hours using a hot plate or the like.
シロップ状アクリル樹脂組成物a100部に対して、さらに連鎖移動剤としてn-ドデカンチオール(nDSH)0.03部を添加したこと以外は、実施例1と同様にして無溶剤型硬化性樹脂組成物を調製し、粘着シートを作製した。 Example 2
A solvent-free curable resin composition as in Example 1 except that 0.03 parts of n-dodecanethiol (nDSH) was further added as a chain transfer agent to 100 parts of the syrupy acrylic resin composition a. Were prepared to prepare a pressure-sensitive adhesive sheet.
シロップ状アクリル樹脂組成物a100部に対して、さらに連鎖移動剤としてn-ドデカンチオール(nDSH)0.03部及びエポキシ系シランカップリング剤(信越化学工業社製、商品名KBM-403)を添加したこと以外は、実施例1と同様にして無溶剤型硬化性樹脂組成物を調製し、粘着シートを作製した。 Example 3
Furthermore, 0.03 parts of n-dodecanethiol (nDSH) as a chain transfer agent and an epoxy-based silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) are added to 100 parts of the syrupy acrylic resin composition a. A solvent-free curable resin composition was prepared in the same manner as in Example 1 except for the above to prepare a pressure-sensitive adhesive sheet.
シロップ状アクリル樹脂組成物aの代わりにシロップ状アクリル樹脂組成物bを使用したこと以外は、実施例3と同様にして無溶剤型硬化性樹脂組成物を調製し、粘着シートを作製した。 Example 4
A non-solvent curable resin composition was prepared in the same manner as in Example 3 except that the syrupy acrylic resin composition b was used instead of the syrupy acrylic resin composition a, to prepare a pressure-sensitive adhesive sheet.
シロップ状アクリル樹脂組成物aの代わりにシロップ状アクリル樹脂組成物cを使用したこと以外は、実施例3と同様にして無溶剤型硬化性樹脂組成物を調製し、粘着シートを作製した。 Example 5
A solventless curable resin composition was prepared in the same manner as in Example 3 except that the syrupy acrylic resin composition c was used instead of the syrupy acrylic resin composition a, to prepare a pressure-sensitive adhesive sheet.
紫外線の照射時間を40秒から120秒間に変更したこと以外は、実施例2と同様にして粘着シートを作製した。 Comparative Example 1
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 2 except that the irradiation time of the ultraviolet light was changed from 40 seconds to 120 seconds.
(粘着剤組成物の調製)
溶剤型アクリル樹脂組成物d100部(固形分50質量%)に対して、架橋剤としてトリメチロールプロパンのトリレンジイソシアネート付加物の55%酢酸エチル溶液(日本ポリウレタン社製、コロネートL-55E)0.2部(固形分50質量%)イソステアリルアクリレート(大阪有機化学工業製、商品名ISTA)20部、ヘキサンジオールジアクリレート(新中村化学工業社製、商品名NKエステルA-HD-N)2部、光重合開始剤(BASFジャパン社製、商品名ダロキュア1173)2部を配合し、粘着剤組成物溶液を得た。 Comparative Example 2 (corresponding to an example of Patent Document 2)
(Preparation of pressure-sensitive adhesive composition)
A 55% ethyl acetate solution of tolylene diisocyanate adduct of trimethylolpropane as a crosslinking agent (100 parts by solid content: 50% by mass) of a solvent type acrylic resin composition d (Coronate L-55E, manufactured by Nippon Polyurethane Co., Ltd.) 0. 2 parts (solid content: 50% by mass) 20 parts of isostearyl acrylate (Osaka Organic Chemical Industry, trade name: ISTA), 2 parts of hexanediol diacrylate (trade name: NK ester A-HD-N, trade name: Shin-Nakamura Chemical Co., Ltd.) 2 parts of a photopolymerization initiator (manufactured by BASF Japan Ltd., trade name Darocure 1173) was blended to obtain a pressure-sensitive adhesive composition solution.
上記粘着剤組成物溶液を、離型剤処理したPETフィルムに、乾燥後の厚みが0.10mmとなるように塗布し、100℃で5分間乾燥し、粘着剤層を形成した。この粘着剤層を離型剤処理したPETフィルムで挟み、40℃で3日間エージングさせて粘着シートを得た。 (Production of adhesive sheet)
The pressure-sensitive adhesive composition solution was applied to a release agent-treated PET film so that the thickness after drying was 0.10 mm, and dried at 100 ° C. for 5 minutes to form a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer was sandwiched by a release-agent-treated PET film and aged at 40 ° C. for 3 days to obtain a pressure-sensitive adhesive sheet.
(粘着剤組成物の調製)
溶剤型アクリル樹脂e100部に、架橋剤として多官能イソシアネート化合物(日本ポリウレタン工業社製、商品名コロネートHL)1.4部を配合し、粘着剤組成物溶液を得た。 Comparative Example 3 (corresponding to an example of Patent Document 1)
(Preparation of pressure-sensitive adhesive composition)
In 100 parts of solvent type acrylic resin e, 1.4 parts of a polyfunctional isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HL) as a crosslinking agent was blended to obtain a pressure-sensitive adhesive composition solution.
上記粘着剤組成物溶液を用いたこと以外は、比較例2と同様にして粘着シートを作製した。 (Production of adhesive sheet)
A pressure-sensitive adhesive sheet was produced in the same manner as in Comparative Example 2 except that the pressure-sensitive adhesive composition solution was used.
「D.1173」:アセトフェノン系光重合開始剤(BASFジャパン社製、商品名ダロキュア1173)
「A-HD-N」:1,6-ヘキサンジオールジアクリレート(新中村化学工業社製、商品名NKエステルA-HD-N)
「nDSH」:n-ドデカンチオール
「KBM-403」:3-グリシドキシプロピルトリエトキシシラン(信越化学工業社製)
「BTZ-M」:ベンゾトリアゾ-ル(共同薬品社製、商品名BTZ-M)
「ISTA」:イソステアリルアクリレート(大阪有機化学工業製、商品名ISTA)
「L-55E」:TDI変性イソシアネート(固形分55%、日本ポリウレタン社製、商品名コロネートL-55E)
「HL」:HDI変性イソシアネート(日本ポリウレタン社製、商品名コロネートHL) The abbreviations in Table 2 are as follows.
"D. 1173": Acetophenone photopolymerization initiator (manufactured by BASF Japan Ltd., trade name Darocure 1173)
"A-HD-N": 1,6-hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester A-HD-N)
"NDSH": n-dodecanethiol "KBM-403": 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
"BTZ-M": Benzotriazole (manufactured by Kyodo Pharmaceutical Co., Ltd., trade name BTZ-M)
"ISTA": Isostearyl Acrylate (Osaka Organic Chemical Industry, trade name ISTA)
"L-55E": TDI modified isocyanate (solid content 55%, manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Coronate L-55E)
"HL": HDI modified isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HL)
実施例及び比較例の粘着シートに対して以下の試験を行った。その結果を表3に示す。 <Evaluation test method>
The following tests were performed to the adhesive sheet of the Example and the comparative example. The results are shown in Table 3.
粘着シートをカバーガラス(0.15mm厚)に貼り付け、高圧水銀灯で800mJ/mm2の紫外線を照射し、硬化させた。その後、剥離フィルムを剥し、HazeメーターにてHaze、色差計にて色味を測定し、Haze=0.6以下、△E*ab=3.2以下を合格(〇)とし、それ以上を不合格(×)とした。 (transparency)
The adhesive sheet was attached to a cover glass (0.15 mm thickness), and was irradiated with ultraviolet light of 800 mJ / mm 2 with a high pressure mercury lamp to be cured. Thereafter, the release film is peeled off, and the color is measured with a Haze meter and a color difference meter. Haze = 0.6 or less, ΔE * ab = 3.2 or less is a pass (o), and no more. Passed (x).
ITO蒸着PETフィルムとカバーガラス(0.15mm厚)とを粘着シートで積層し、高圧水銀灯で800mJ/mm2の紫外線を照射し、硬化させた。その後、85℃、85%RHの雰囲気下に250時間放置し、室温に1時間放置し、白化を目視で確認した。また、湿熱放置前後のHazeを測定し、値の変化が20%未満を合格(○)とし、それ以上を不合格(×)とした。 (Moisture resistant whitening resistance)
An ITO-deposited PET film and a cover glass (0.15 mm thickness) were laminated with an adhesive sheet, and were irradiated with ultraviolet light of 800 mJ / mm 2 with a high pressure mercury lamp to be cured. Thereafter, it was left for 250 hours in an atmosphere at 85 ° C. and 85% RH, left at room temperature for 1 hour, and whitening was visually confirmed. In addition, Haze before and after being left moist heat was measured, and a change of the value of less than 20% was taken as pass (o), and more than that was taken as fail (x).
電極部分としてAgペーストを塗布したITO蒸着PETフィルム(東洋紡社製、商品名300RK)に、基材無し粘着シートを貼り合せ、反対側の面にPETフィルムを貼り合せたサンプルを、高圧水銀灯で800mJ/mm2の紫外線を照射し、硬化させた。その後65℃、90%RH雰囲気下に500時間放置し、粘着シートを貼り合せていないITOフィルムをブランクとして、マルチメーターにて促進前後の抵抗値を測定し、ブランクとの抵抗値変化率が20%以内を合格(○)とし、それ以上を不合格(×)とした。 (ITO resistance to conductive deterioration)
A substrateless adhesive sheet is bonded to an ITO-deposited PET film (trade name: 300RK, manufactured by Toyobo Co., Ltd.) coated with Ag paste as an electrode portion, and a sample obtained by bonding a PET film to the opposite side is 800 mJ with a high pressure mercury lamp It was irradiated with ultraviolet rays / mm 2 and cured. Then, it is left to stand in a 65 ° C., 90% RH atmosphere for 500 hours, the resistance value before and after promotion is measured with a multimeter, using an ITO film not attached with an adhesive sheet as a blank. A percentage (%) was given as a pass (○), and more than this was given as a rejection (×).
粘着シートをガラス板貼り付け、その反対側にPET#125を貼り付け、積層サンプルを作製した。この積層サンプルに高圧水銀灯で800mJ/mm2の紫外線を照射し、硬化させた。その後85℃、85%RHの雰囲気下に250時間放置し、積層した部分の発泡、浮きがないことを目視で確認した。浮き及び気泡が無いものを合格(○)とし、浮き又は気泡有るものを不合格(×)とした。 (Foam resistance)
A pressure-sensitive adhesive sheet was attached to a glass plate, and PET # 125 was attached to the opposite side to prepare a laminated sample. The laminated sample was irradiated with ultraviolet light of 800 mJ / mm 2 with a high pressure mercury lamp to be cured. Then, it was left to stand in an atmosphere of 85 ° C. and 85% RH for 250 hours, and it was visually confirmed that there was no foaming or floating of the laminated portion. Those with no float and no bubble were regarded as pass (○), and those with float or bubble were regarded as fail (×).
ガラス板の上に、段差として所定の厚さで、幅10mmのL字型に切り抜いたフィルムを置き、粘着シート(40mm×50mm)で段差を挟むようにガラス板に貼付け、その反対側にPET#125を貼り付け、積層サンプルを作製した。この積層サンプルをオートクレーブにて60℃、0.5MPa×30分間加熱加圧し、高圧水銀灯で800mJ/mm2の紫外線を照射し硬化させた。硬化させた積層体を85℃、85%RHの雰囲気下に250時間放置し、段差の周りに浮きや気泡のないことを目視で確認した。浮き及び気泡が無いものを合格(○)とし、浮き又は気泡有るものを不合格(×)とした。 (Step absorbability)
Place a L-shaped film cut out with a width of 10 mm in a predetermined thickness as a step on a glass plate, and stick it on the glass plate with a pressure-sensitive adhesive sheet (40 mm x 50 mm) to sandwich the step. The laminated sample was produced by sticking # 125. The laminated sample was heated and pressurized in an autoclave at 60 ° C., 0.5 MPa × 30 minutes, and irradiated with ultraviolet light of 800 mJ / mm 2 with a high pressure mercury lamp to be cured. The cured laminate was allowed to stand in an atmosphere of 85 ° C. and 85% RH for 250 hours, and visually confirmed that there were no floating or bubbles around the step. Those with no float and no bubble were regarded as pass (○), and those with float or bubble were regarded as fail (×).
粘着シート(25mm幅)をガラス板に貼り付け、その反対側にPET#125を貼り付け、積層サンプルを作製した。この積層サンプルに高圧水銀灯で800mJ/mm2の紫外線を照射し硬化させた。その2時間後に、引っ張り試験機にて、PETフィルムと粘着シートをガラス板に対して90°方向に、300mm/minの速度で剥がし、そのときの粘着力を測定した。 (90 ° adhesion to glass)
A pressure-sensitive adhesive sheet (25 mm width) was attached to a glass plate, and PET # 125 was attached to the opposite side to prepare a laminated sample. The laminated sample was irradiated with ultraviolet light of 800 mJ / mm 2 with a high pressure mercury lamp to be cured. Two hours later, the PET film and the adhesive sheet were peeled off at a speed of 300 mm / min in the direction of 90 ° with respect to the glass plate with a tensile tester, and the adhesion at that time was measured.
粘着シート25mm幅をガラス板貼り付け、その反対側にPET#125を貼り付け、積層サンプルを作製した。作製した積層サンプルに高圧水銀灯で800mJ/mm2の紫外線を照射し、硬化させた。その後90℃雰囲気下に72時間放置し、取り出し2時間後に、PETフィルムと粘着シートをガラス板に対して90°方向に300mm/minの速度で剥がし、ガラス板への糊残りの有無を確認した。 (Reworkability)
A pressure-sensitive adhesive sheet of 25 mm in width was attached to a glass plate, and PET # 125 was attached to the opposite side to prepare a laminated sample. The produced laminated sample was irradiated with ultraviolet light of 800 mJ / mm 2 with a high pressure mercury lamp to be cured. Thereafter, it was left for 72 hours in a 90 ° C. atmosphere, and after 2 hours of removal, the PET film and the adhesive sheet were peeled off at a speed of 300 mm / min in the 90 ° direction to the glass plate to confirm the presence or absence of adhesive residue on the glass plate .
表3に示すように、実施例1~5の粘着シートは、段差吸収性、リワーク性に優れ、なお且つ、光学部材用粘着剤として要求される特性を兼ね備えており、高温高湿環境下でも安定した接着力を得られた。 <Evaluation>
As shown in Table 3, the pressure-sensitive adhesive sheets of Examples 1 to 5 are excellent in step absorptivity and reworkability, and also have the properties required as a pressure-sensitive adhesive for optical members, even in a high temperature and high humidity environment. Stable adhesion was obtained.
Claims (10)
- 粘着剤層を有する粘着シートであって、
前記粘着剤層が、分子中に不飽和二重結合を1つのみ有する(メタ)アクリル酸エステル(A)50~85質量%及び分子中に不飽和二重結合を1つのみ有する水酸基含有(メタ)アクリル酸エステル(B)15~50質量%を含むモノマー組成物を塊状重合法により部分重合して得られるシロップ状アクリル樹脂組成物と、多官能性(メタ)アクリレート化合物(C)と、光重合開始剤とを含む無溶剤型硬化性樹脂組成物を活性エネルギー線の照射により硬化して形成した層であり、
前記粘着剤層中に、未反応の(メタ)アクリレート化合物(A)及び(B)が部分的に残存している粘着シート。 A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer,
The pressure-sensitive adhesive layer contains 50 to 85% by mass of (meth) acrylic acid ester (A) having only one unsaturated double bond in the molecule and a hydroxyl group-containing compound having only one unsaturated double bond in the molecule ( A syrupy acrylic resin composition obtained by partial polymerization of a monomer composition containing 15 to 50% by mass of a meta) acrylic ester (B) by bulk polymerization, and a polyfunctional (meth) acrylate compound (C), It is a layer formed by curing a solventless curable resin composition containing a photopolymerization initiator by irradiation with active energy rays,
A pressure-sensitive adhesive sheet in which unreacted (meth) acrylate compounds (A) and (B) partially remain in the pressure-sensitive adhesive layer. - モノマー組成物中の水酸基含有(メタ)アクリル酸エステル(B)が、(メタ)アクリル酸2-ヒドロキシエチル及び(メタ)アクリル酸4-ヒドロキシブチルを質量比1:5~5:1の割合で含む請求項1記載の粘着シート。 The hydroxyl group-containing (meth) acrylic acid ester (B) in the monomer composition contains 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate in a mass ratio of 1: 5 to 5: 1. The pressure-sensitive adhesive sheet according to claim 1, which comprises.
- 無溶剤型硬化性樹脂組成物が、さらにシランカップリング剤、連鎖移動剤及びベンゾトリアゾール系防錆剤を含む請求項1記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the solvent-free curable resin composition further contains a silane coupling agent, a chain transfer agent and a benzotriazole-based rust inhibitor.
- 粘着剤層の厚さが5~500μmである請求項1記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the thickness of the pressure-sensitive adhesive layer is 5 to 500 μm.
- 粘着剤層を有する粘着シートの製造方法であって、
分子中に不飽和二重結合を1つのみ有する(メタ)アクリル酸エステル(A)50~85質量%及び分子中に不飽和二重結合を1つのみ有する水酸基含有(メタ)アクリル酸エステル(B)15~50質量%を含むモノマー組成物を塊状重合法により部分重合して得られるシロップ状アクリル樹脂組成物と、多官能性(メタ)アクリレート化合物(C)と、光重合開始剤を含む無溶剤型硬化性樹脂組成物を調製する工程(1)、並びに、
前記無溶剤型硬化性樹脂組成物を活性エネルギー線の照射により硬化して、未反応の(メタ)アクリレート化合物(A)及び(B)が部分的に残存している粘着剤層を形成する工程(2)
を有する粘着シートの製造方法。 It is a manufacturing method of a pressure sensitive adhesive sheet which has a pressure sensitive adhesive layer,
(Meth) acrylic acid ester (A) having only one unsaturated double bond in the molecule (A) 50 to 85% by mass and hydroxyl group-containing (meth) acrylic acid ester having only one unsaturated double bond in the molecule ( B) A syrupy acrylic resin composition obtained by partially polymerizing a monomer composition containing 15 to 50% by mass by bulk polymerization, a multifunctional (meth) acrylate compound (C), and a photopolymerization initiator A step (1) of preparing a solventless curable resin composition, and
A step of curing the non-solvent type curable resin composition by irradiation with active energy rays to form a pressure-sensitive adhesive layer in which unreacted (meth) acrylate compounds (A) and (B) partially remain (2)
The manufacturing method of the adhesive sheet which has. - 粘着シートを用いて接着された部品を含む光学部材の製造方法であって、
請求項1記載の粘着シートを用いて被接着物を貼り合わせる工程(3)、並びに、
前記被接着物を貼り合わせた後の粘着シートの粘着剤層に活性エネルギー線を照射することにより、粘着剤層中に残存する未反応の(メタ)アクリレート化合物(A)及び(B)を重合させて完全接着する工程(4)
を有する光学部材の製造方法。 What is claimed is: 1. A method of manufacturing an optical member comprising a component adhered using an adhesive sheet, comprising:
A step (3) of bonding the adherends together using the pressure-sensitive adhesive sheet according to claim 1;
The unreacted (meth) acrylate compounds (A) and (B) remaining in the pressure-sensitive adhesive layer are polymerized by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet after bonding the adherends with an active energy ray. To completely bond them (4)
A method of manufacturing an optical member comprising: - 工程(3)において、粘着シートを介して加圧、又は加熱しながら加圧して被接着物を貼り合わせる請求項6記載の光学部材の製造方法。 The method for producing an optical member according to claim 6, wherein in the step (3), the adherends are bonded by applying pressure or heat via the pressure-sensitive adhesive sheet.
- 工程(3)において、被接着物の接着面の少なくとも一部が、3~100μmの段差を有する請求項6記載の光学部材の製造方法。 The method for producing an optical member according to claim 6, wherein in the step (3), at least a part of the adhesive surface of the adherend has a step of 3 to 100 μm.
- 光学部材が、3~100μmの段差による装飾用印刷の施された、ガラス又はポリエチレンテレフタレートフィルムからなる請求項8記載の光学部材の製造方法。 The method for producing an optical member according to claim 8, wherein the optical member comprises a glass or a polyethylene terephthalate film subjected to decorative printing with a step of 3 to 100 μm.
- 光学部材が、画像表示装置又はタッチパネルに用いられる部材である請求項1記載の光学部材の製造方法。 The method according to claim 1, wherein the optical member is a member used for an image display device or a touch panel.
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JPWO2016117045A1 (en) | 2017-08-17 |
CN107207914A (en) | 2017-09-26 |
KR101927012B1 (en) | 2018-12-07 |
KR20170085095A (en) | 2017-07-21 |
CN107207914B (en) | 2020-10-16 |
JP6479856B2 (en) | 2019-03-06 |
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