JP2016141687A - Optical transparent adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical transparent adhesive sheet having excellent adhesive properties even under cold temperature-cold humidity, and in which a shape change under high temperature-high moisture is less likely to occur.SOLUTION: Provided is an optical transparent adhesive sheet made of a cured matter of a thermocurable polyurethane composition, in which the thermocurable comprises a polyol component, a polyisocyanate component and a tackifier, and the tackifier includes a rosin-diol based tackifier.SELECTED DRAWING: Figure 1

Description

The present invention relates to an optically transparent adhesive sheet.

An optical transparent adhesive (OCA) sheet is a transparent adhesive sheet used for bonding optical members. In recent years, the demand for touch panels in the fields of smartphones, tablet PCs, portable game machines, car navigation devices, etc. has increased rapidly, and accordingly, demand for OCA sheets used for bonding touch panels to other optical members is increasing. Has also increased. A display device provided with a touch panel is usually a display panel such as a liquid crystal panel, a transparent member (touch panel body) having a transparent conductive film made of ITO (indium tin oxide) or the like as a surface layer, and a cover for protecting the transparent conductive film It has a structure in which optical members such as panels are laminated, and an OCA sheet is used for bonding between optical members. However, since there is a bezel that is the housing of the display panel between the display panel and the touch panel body, it is wider than the interval of the other optical members and is not bonded by the OCA sheet, and an air layer called an air gap It was common to provide.

As an OCA sheet, for example, a sheet made of a silicone resin composition or an acrylic resin composition is known. However, since the OCA sheet using a silicone resin has low adhesive strength, air may enter between the optical members, and the visibility of the display screen may be reduced, for example. In an OCA sheet using an acrylic resin, there is a problem that acrylic acid remaining in the acrylic resin or an acid component generated by hydrolysis corrodes a metal used in the optical member. In addition, when the acrylic resin composition is an ultraviolet curable resin composition, free radicals necessary for the reaction are consumed in the surface layer portion of the acrylic resin during ultraviolet irradiation, and the bottom portion becomes uncured. It was difficult to obtain a thick OCA sheet.

Patent Document 1 discusses the use of a thermosetting polyurethane resin composition. By using hydrogenated dimer diol and hydroxyl group-terminated hydrogenated polybutadiene at a specific mass ratio, transparency, foam breaking It is disclosed that a pressure-sensitive adhesive film satisfying properties, tackiness, whitening resistance and flexibility can be obtained.

JP 2013-18856 A

When an air gap, which is an air layer, exists between the optical members, interface reflection occurs due to a difference in refractive index between the air layer and the optical member, thereby reducing the visibility of the display panel. For this reason, a thick-film OCA sheet suitable for bonding the display panel and the touch panel body has been demanded. Further, the OCA sheet used for bonding the display panel and the touch panel body is also required to fill a step formed by the thickness of the bezel. Therefore, an OCA sheet that is excellent in flexibility (step following ability) and that can be thickened is required.

Further, an important characteristic required for the OCA sheet is an adhesive strength, and an adhesive strength to glass is generally used as an evaluation index. The OCA sheet is required to have no change in physical properties even when the usage environment changes, and the adhesive strength is sufficient not only at room temperature and normal humidity but also at high temperature and high humidity. Is required. However, the conventional OCA sheet has a tendency that the adhesive strength is remarkably lowered at high temperature and high humidity.

In view of the above, there is a demand for an OCA sheet that is excellent in flexibility (step following ability), can be thickened, and has excellent adhesiveness not only at room temperature and normal humidity but also at high temperature and high humidity. It was.

In the present specification, normal temperature and normal humidity refer to a temperature of 23 ° C. and humidity of 50%, and high temperature and high humidity refer to a temperature of 85 ° C. and humidity of 85%.

The present inventors have focused on a non-solvent thermosetting polyurethane composition as a material for an OCA sheet that is excellent in flexibility (step difference followability) and can be made thick. And in order to make adhesive strength of an OCA sheet sufficient under high temperature and high humidity, adding the tackifier (tackifier) to the thermosetting polyurethane resin composition was examined. However, since the tackifier is a material having a relatively low polarity, it has been difficult to sufficiently obtain compatibility with a urethane raw material that is a material having a relatively high polarity. For example, compatibility could be improved by using a tackifier in which the side chain of rosin was modified with a carboxyl group, but the condensation reaction between the polyol component and the polyisocyanate component was inhibited, and part of the obtained OCA sheet Another problem arises in that it dissolves under high humidity and high temperature.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have added rosin-based tackifier as a tackifier to the thermosetting polyurethane resin composition, so that not only at normal temperature and normal humidity but also at high temperature and high humidity. The present invention was completed by finding that an OCA sheet having excellent adhesiveness even under humidity and not impeding the reactivity of urethane so that it does not dissolve even under high humidity and high temperature can be obtained.

The optically transparent adhesive sheet of the present invention is an optically transparent adhesive sheet made of a cured product of a thermosetting polyurethane composition, and the thermosetting polyurethane composition contains a polyol component, a polyisocyanate component, and a tackifier. The tackifier includes a rosin diol tackifier.

The thermosetting polyurethane composition preferably has an α ratio (number of moles of OH group derived from polyol component / number of moles of NCO group derived from polyisocyanate component) of 1 or more, and further contains a monoisocyanate component.

The thickness of the optically transparent adhesive sheet is preferably 50 μm or more and 2000 μm or less.

The optically transparent pressure-sensitive adhesive sheet of the present invention has excellent adhesiveness not only at normal temperature and normal humidity but also at high temperature and high humidity, and is less likely to change its shape under high temperature and high humidity. In addition, the optically transparent adhesive sheet of the present invention can be easily thickened, and is excellent in transparency, flexibility (step following ability), and tensile strength.

It is sectional drawing which showed typically an example of the display apparatus with a touch panel using the optically transparent adhesive sheet of this invention. It is a schematic diagram for demonstrating an example of the shaping | molding apparatus used for preparation of the optical transparent adhesive sheet of this invention. It is sectional drawing which showed typically the optical transparent adhesive sheet with a double-sided protective film of Example 1. FIG. It is a schematic diagram for demonstrating the evaluation method of the adhesive force of the optically transparent adhesive sheet of an Example and a comparative example.

The optically transparent adhesive sheet of the present invention is an optically transparent adhesive sheet made of a cured product of a thermosetting polyurethane composition, and the thermosetting polyurethane composition contains a polyol component, a polyisocyanate component, and a tackifier. The tackifier includes a rosin diol tackifier. In the present specification, “optically transparent adhesive sheet” has the same meaning as “optically transparent adhesive film”.

The said optically transparent adhesive sheet consists of hardened | cured material of a thermosetting polyurethane composition, and the said thermosetting polyurethane composition contains a polyol component and a polyisocyanate component. The cured product of the thermosetting polyurethane composition is obtained by reacting a polyol component and a polyisocyanate component, and has a structure represented by the following formula (A).

In said formula (A), R represents the site | part except the NCO group of the polyisocyanate component, R 'represents the site | part except the OH group of the polyol component, and n represents the number of repeating units.

The cured product of the thermosetting polyurethane composition is preferably not acrylic-modified, and it is preferable that the main chain does not contain a site derived from an acrylate ester, a methacrylate ester, or the like. Since it is hydrophobized when it is acrylic-modified, moisture aggregation tends to occur at high temperatures and high humidity. This agglomeration of water causes whitening, foaming and the like and impairs optical properties. Therefore, by making it not acrylic-modified, it is possible to prevent deterioration of optical properties due to whitening, foaming, etc. at high temperature and high humidity.

As the polyol component and the polyisocyanate component, those that are liquid at normal temperature (23 ° C.) can be used, and a cured product of a thermosetting polyurethane composition can be obtained without using a solvent. Other components such as a tackifier can be added to either the polyol component or the polyisocyanate component, and are preferably added to the polyol component. Thus, when producing an optically transparent adhesive sheet with a cured product of a thermosetting polyurethane composition, it is not necessary to remove the solvent, so that a uniform sheet can be formed thick. Thereby, when it uses for bonding with the transparent panel (touch panel) which has a display panel and a transparent conductive film in a surface layer, the level | step difference of a bezel can be coat | covered. In addition, the optically transparent adhesive sheet of the present invention can maintain optical properties even when it is formed thick, and the transparency (haze) decreases, coloration, foaming (bubble generation at the interface with the adherend) ) Can be sufficiently suppressed.

The optically transparent pressure-sensitive adhesive sheet is made of a cured product of a thermosetting polyurethane composition, and is flexible, so that it stretches well when subjected to a tensile stress and is very difficult to break. For this reason, it is possible to peel off without leaving glue. Furthermore, since the optical transparent adhesive sheet is flexible and can be thickened, it has excellent impact resistance, and when a transparent member having a transparent conductive film on its surface is bonded to a cover panel, and when other members are used. It can also be used for bonding a display panel or a transparent member having a transparent conductive film as a surface layer to another member. Furthermore, since the optically transparent adhesive sheet of the present invention is made of a cured product of a thermosetting polyurethane composition, it has a high dielectric constant and a higher capacitance than that of an optically transparent adhesive sheet made of a conventional acrylic resin composition. Therefore, it is suitably used for bonding of capacitive touch panels.

[Polyol component]
It does not specifically limit as said polyol component, For example, polyether polyol, polycaprolactone polyol, polycarbonate polyol, polyester polyol etc. are mentioned.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polypropylene triol, polypropylene tetraol, polytetramethylene glycol, polytetramethylene triol, polyalkylene glycols such as copolymers thereof, and side chains introduced into these. And derivatives having a branched structure introduced therein, modified products, and mixtures thereof.

Examples of the polycaprolactone polyol include polycaprotectone glycol, polycaprolactone triol, polycaprolactone tetraol, derivatives in which side chains are introduced or branched structures are introduced, modified products, and mixtures thereof. Can be mentioned.

As said polycarbonate polyol, the reaction material of a dialkyl carbonate and diol is mentioned, for example.

Examples of the dialkyl carbonate include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, diaryl carbonates such as diphenyl carbonate, and alkylene carbonates such as ethylene carbonate. These may be used alone or in combination of two or more.

Examples of the diol include 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 2-methyl-1,8. -Octanediol, 1,9-nonanediol, 1,10-dodecanediol, 2-ethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5- Examples include pentanediol, neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2′-bis (4-hydroxycyclohexyl) -propane, and the like. These may be used alone or in combination of two or more. As said diol, C4-C9 alicyclic or alicyclic diol is preferable, for example, 1, 4- butane diol, diethylene glycol, 1, 5- pentane diol, 1, 6-hexane diol, 3- Methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1 , 8-octanediol and 1,9-nonanediol are preferably used alone or in combination of two or more. Examples of the diol include a copolycarbonate diol composed of 1,6-hexanediol and 3-methyl-1,5-pentanediol, and a copolycarbonate diol composed of 1,6-hexanediol and 1,5-pentanediol. Is also preferable.

Further, as the polycarbonate polyol, for example, polycarbonate glycol, polycarbonate triol, polycarbonate tetraol, derivatives in which side chains are introduced or branched structures are introduced therein, modified products, and mixtures thereof may be used. it can.

As said polyester polyol, what dehydrated and condensed dicarboxylic acid and the glycol component is mentioned, for example.

Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. Can be mentioned.

Examples of the glycol component include ethylene glycol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,9-nonanediol, Aliphatic glycols such as ethylene glycol, alicyclic glycols such as 1,4-cyclohexanedimethanol, aromatic diols such as p-xylene diol, polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol Can be mentioned.

The polyester polyol formed by the dicarboxylic acid and the glycol component exemplified above has a linear molecular structure, but the polyester polyol has a branched molecular structure using a trivalent or higher ester-forming component. It may be. What is necessary is just to make the said dicarboxylic acid and the said glycol component react at 150-300 degreeC by molar ratio 1.1-1.3.

As the polyol component, polycarbonate polyol is preferable. It is because it is excellent in hydrolysis resistance, mechanical characteristics, and chemical resistance. Moreover, the said polyol component may use only 1 type and may use 2 or more types together.

The polyol component preferably has a number average molecular weight of 300 to 5,000. When the number average molecular weight of the polyol component is less than 300, the reaction between the polyol component and the polyisocyanate component is too fast, making it difficult to form a cured product of the thermosetting polyurethane resin composition into a uniform sheet. Or the flexibility of the cured product of the thermosetting polyurethane resin composition may be reduced and become brittle. When the number average molecular weight of the polyol component exceeds 5,000, the viscosity of the polyol component becomes too high, making it difficult to form a cured product of the thermosetting polyurethane resin composition into a uniform sheet, or thermosetting. In some cases, the cured product of the polyurethane resin composition may crystallize and become cloudy. A more preferable number average molecular weight of the polyol is 500 to 2,000.

[Polyisocyanate component]
It does not specifically limit as said polyisocyanate component, A conventionally well-known polyisocyanate can be used. As the polyisocyanate component, aliphatic polyisocyanate (including alicyclic polyisocyanate) is preferable. This is because coloring and discoloration of the optical transparent pressure-sensitive adhesive sheet are less likely to occur, and the transparency of the optical transparent pressure-sensitive adhesive sheet can be more reliably ensured over a long period of time.

Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate (HDI), hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, lysine diisocyanate, isopropylidenebis (4-cyclohexyl isocyanate), and norbornane. Examples thereof include diisocyanates, modified products and multimers thereof. These may be used alone or in combination of two or more. As said aliphatic polyisocyanate, hexamethylene diisocyanate or its modified body, and isophorone diisocyanate are preferable, and hexamethylene diisocyanate and its modified body are especially preferable. In addition, as the modified product of hexamethylene diisocyanate, specifically, for example, hexamethylene diisocyanate modified with isocyanurate, allophanate and / or urethane, and having an average functional group number of 2.0 or more, etc. It is done.

The thermosetting polyurethane composition preferably has an α ratio (number of moles of OH group derived from polyol component / number of moles of NCO group derived from polyisocyanate component) of 1 or more. When the α ratio is less than 1, the blended amount of the polyisocyanate component is excessive with respect to the blended amount of the polyol component, so that the cured product of the thermosetting polyurethane composition becomes hard and optically transparent adhesive It becomes difficult to ensure the flexibility (step following capability) required for the sheet. When the flexibility is low, it is not possible to cover the unevenness and the step existing on the bonding surface particularly by bonding of an optical member such as a touch panel. Moreover, the adhesive strength under high temperature and high humidity cannot be ensured. The α ratio is more preferably 1 <α <1.5. When the α ratio is 1.5 or more, the thermosetting polyurethane composition may not be cured.

[Tackfire]
The thermosetting polyurethane composition further contains a tackifier (tackifier). A tackifier is an additive added to improve adhesiveness, and is usually an amorphous oligomer having a molecular weight of hundreds to thousands, and is a thermoplastic resin that is liquid or solid at room temperature. By containing the tackifier, the optically transparent adhesive sheet made of a cured product of the thermosetting polyurethane composition has sufficient adhesiveness on both sides thereof.

The tackifier includes a rosin diol tackifier. Only one type of rosin diol tackifier may be included, or two or more types thereof may be included. When the tackifier contains a rosin diol tackifier, the compatibility with the thermosetting polyurethane composition is improved, and the effect of preventing the adhesive strength of the resulting optically transparent adhesive sheet from decreasing at high temperatures and high humidity is obtained. It is done. The tackifier may include other types of tackifiers such as rosin tackifiers other than rosindiol, terpene tackifiers, petroleum tackifiers, and the like.

Even in the case of a rosin acid derivative, a compound having a high acid value in which the side chain is modified with a carboxyl group inhibits the condensation reaction between the polyol component and the polyisocyanate component. If the condensation reaction between the polyol component and the polyisocyanate component is inhibited, the crosslinking reaction of urethane does not proceed completely, and there is a problem that a part of the obtained optically transparent adhesive sheet is dissolved at high temperature and high humidity. . In particular, in the present invention, the α ratio is set to 1 or more to ensure the flexibility (step following ability) required for the optical transparent pressure-sensitive adhesive sheet. It is easy for dissolution to occur. On the other hand, since the rosin diol tackifier does not inhibit the condensation reaction between the polyol component and the polyisocyanate component, it is possible to prevent dissolution of the optically transparent adhesive sheet under high temperature and high humidity.

Examples of the rosin diol tackifier include derivatives of compounds represented by the following chemical formulas (1) to (8).

The rosin diol tackifier is obtained, for example, by reacting the compounds represented by the chemical formulas (1) to (8) with an acid or an anhydride, and then reducing the diol. Examples of the acid to be reacted with the compounds represented by the above chemical formulas (1) to (8) include acrylic acid, maleic acid, fumaric acid, itaconic acid, and the like, and a mixture thereof. For example, maleic anhydride, fumaric anhydride, itaconic anhydride and the like, and mixtures thereof can be mentioned. For the reaction with the acid or anhydride, conditions and methods known in the art can be used. For the reduction to the diol, a known reduction method such as a method using hydrogen and a platinum catalyst or a method using a reducing agent such as lithium aluminum hydride can be used.

As a well-known thing among the said rosin diol-type tackifiers, "KE-601", "D-6011", "KE-615-3" by Arakawa Chemical Co., Ltd. etc. can be used, for example.

The rosin diol tackifier preferably has an acid value of 1 mgKOH / g or less. When the acid value is 1 mgKOH / g or less, the rosin diol tackifier can be sufficiently prevented from inhibiting the reactivity of the polyol component and the polyisocyanate component. The rosin diol tackifier preferably has a softening point of 80 to 120 ° C, and more preferably 80 to 100 ° C. When the softening point is 80 to 120 ° C., the polyol component can be sufficiently prevented from being deteriorated by heat when the rosin diol tackifier is dissolved in the polyol component.

The content of the tackifier is 1 to 20% by weight with respect to the thermosetting polyurethane composition. Preferably, the content of the rosin diol tackifier is based on the thermosetting polyurethane composition. 1 to 20% by weight. When the content of the tackifier is less than 1% by weight, the adhesiveness of the optically transparent adhesive sheet may not be sufficiently improved, and the adhesiveness particularly at high temperature and high humidity may be insufficient. When the content of the tackifier exceeds 20% by weight, the reaction between the polyol component and the polyisocyanate component is inhibited, and urethane crosslinking may not be sufficiently formed in the cured product of the thermosetting polyurethane composition. As a result, the optical transparent pressure-sensitive adhesive sheet melts (melts) at high temperature and high humidity to cause a shape change, and tackifier deposition (bleed) occurs. Further, when the reaction time of the polyol component and the polyisocyanate component is lengthened in order to sufficiently form urethane crosslinks, the productivity is lowered.

[Monoisocyanate component]
The thermosetting polyurethane composition may further contain a monoisocyanate component. Thereby, adhesiveness can be improved also under high temperature and high humidity, ensuring the softness | flexibility requested | required of an optical transparent adhesive sheet. When the α ratio of the thermosetting polyurethane composition is 1 or more, a monoisocyanate component is preferably used in order to prevent unreacted OH groups from remaining in the cured product.

The monoisocyanate component is a compound having one isocyanate group in the molecule, and specific examples thereof include, for example, octadecyl diisocyanate (ODI), 2-methacryloyloxyethyl isocyanate (MOI), 2-acryloyloxyethyl isocyanate. (AOI), octyl isocyanate, heptyl isocyanate, ethyl 3-isocyanatopropionate, cyclopentyl isocyanate, cyclohexyl isocyanate, 2-methoxyethane isocyanate, ethyl isocyanate acetate, butyl isocyanate acetate, p-toluenesulfonyl isocyanate, etc. Is mentioned. These may be used alone or in combination of two or more. As the monoisocyanate, 2-methacryloyloxyethyl isocyanate (MOI) is preferable. This is because the compatibility with the polyol component is good and the hydrophobicity is high.

In the thermosetting polyurethane composition, the molar ratio of the isocyanate group derived from the monoisocyanate component is less than 35 mol% with respect to the total amount of the isocyanate group derived from the polyisocyanate component and the isocyanate group derived from the monoisocyanate component. Preferably there is. When the molar ratio is 35 mol% or more, the thermosetting polyurethane composition may be insufficiently cured. The molar ratio is preferably 10 mol% or more. If the molar ratio is less than 10 mol%, the effect of improving the adhesiveness under high temperature and high humidity by adding the monoisocyanate component may not be sufficiently obtained.

The thermosetting polyurethane composition may further contain a catalyst. The catalyst is not particularly limited as long as it is a catalyst used in the urethanization reaction. For example, organic tin compounds such as di-n-butyltin dilaurate, dimethyltin dilaurate, dibutyltin oxide, and octane tin; Examples include titanium compounds; organic zirconium compounds; carboxylic acid tin salts; carboxylic acid bismuth salts; and amine-based catalysts such as triethylenediamine.

As the catalyst, a non-amine catalyst is preferable. When an amine system is used as a catalyst, the optical transparent pressure-sensitive adhesive sheet may be easily discolored. A more preferred catalyst is dimethyltin dilaurate.

The addition amount of the said catalyst is 0.01 to 0.1 weight% with respect to the total amount of a polyol component and a polyisocyanate component, for example.

In the thermosetting polyurethane composition, a colorant, a light stabilizer, a heat stabilizer, an antioxidant, an antifungal agent, a flame retardant, etc. These various additives may be contained.

Although the thickness of the said optically transparent adhesive sheet is not specifically limited, It is preferable that they are 50 micrometers or more and 2000 micrometers or less. When the thickness is less than 50 μm, when one surface of the optical transparent pressure-sensitive adhesive sheet is attached to the surface of the optical member, the optical transparent pressure-sensitive adhesive sheet fills the unevenness or level difference present on the surface of the optical member. In some cases, the other surface of the optical transparent pressure-sensitive adhesive sheet and the surface of another optical member cannot be bonded together with sufficient adhesive force. When the thickness exceeds 2000 μm, optical performance such as haze and total light transmittance may not be sufficiently obtained. The more preferable lower limit of the thickness of the optically transparent adhesive sheet is 100 μm, the more preferable upper limit is 1500 μm, the still more preferable lower limit is 200 μm, and the still more preferable upper limit is 1000 μm. Moreover, it is preferable to have a thickness of 3 times or more with respect to the height of the unevenness or level difference present on the pasting surface.

In order to ensure the performance as the optical transparent adhesive sheet, the optical transparent adhesive sheet preferably has a haze of 1% or less and a total light transmittance of 90% or more. Haze and total light transmittance can be measured using, for example, HazeMeter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The haze is measured by a method according to JIS K 7136, and the total light transmittance is measured by a method according to JIS K 7361-1.

The optically transparent pressure-sensitive adhesive sheet preferably has an adhesive strength measured by a 180 ° peel test of 1.0 N / 25 mm or more in both ambient conditions of normal temperature and normal humidity and high temperature and high humidity. This is because, if there is an adhesive strength of 1.0 N / 25 mm or more, the required characteristics as an optical transparent adhesive sheet for touch panels can be satisfied. On the other hand, when the adhesive strength is less than 1.0 N / 25 mm, partial floating (peeling) occurs during use, and as a result, optical performance may be deteriorated. The adhesive strength in the peel test is more preferably 4 N / 25 mm or more and 15 N / 25 mm or less under both ambient conditions of normal temperature / normal humidity and high temperature / high humidity. When the adhesive strength is 15 N / 25 mm or less, when used for bonding optical members such as a touch panel, it can be peeled off without any adhesive residue, so that it has excellent reworkability. Moreover, when the said adhesive force becomes large too much, it may become difficult to remove the bubble which entered between the said optically transparent adhesive sheet and a to-be-adhered body. The details of the 180 ° peel test method will be described later.

The optical transparent pressure-sensitive adhesive sheet preferably has a micro rubber A hardness of 0.5 to 25 °. When the micro rubber A hardness is less than 0.5 °, the handleability at the time of use (at the time of application to an optical member) is poor, and the pressure-sensitive adhesive sheet may be deformed. On the other hand, when the hardness of the micro rubber A exceeds 25 °, the flexibility is low, and when the micro rubber A is attached to the optical member, it cannot follow the surface shape of the optical member, so that air is caught or the optical member May cause peeling. In addition, when the flexibility is low, the step of the bezel may not be covered particularly by bonding of an optical member such as a touch panel. A more preferable micro rubber A hardness is 0.5 to 15 °. The micro rubber A hardness can be measured by, for example, a micro rubber hardness meter MD-1 type A manufactured by Kobunshi Keiki Co., Ltd. The micro rubber hardness tester MD-1 Type A is a hardness tester designed and manufactured as a reduced model of about 1/5 of the spring type rubber hardness tester (durometer) A type. A measured value consistent with the hardness of the spring rubber hardness tester A type can be obtained.

Although the use of the optically transparent adhesive sheet of this invention is not specifically limited, For example, a display panel, a touch panel, a cover panel etc. can be used in order to mutually bond. FIG. 1 is a cross-sectional view schematically showing an example of a display device with a touch panel using the optically transparent adhesive sheet of the present invention. In the display device 10 shown in FIG. 1, a display panel 11, an optical transparent adhesive sheet 12, a touch panel (glass substrate with an ITO transparent conductive film) 13, an optical transparent adhesive sheet 12, and a transparent cover panel 14 are laminated in this order. Yes. Three optical members of the display panel 11, the touch panel 13, and the transparent cover panel 14 are integrated by two optical transparent adhesive sheets 12 of the present invention. The type of the display panel 11 is not particularly limited, and for example, a liquid crystal panel, an organic electroluminescence panel (organic EL panel), or the like can be used.

The display panel 11 is housed in a bezel (a housing of the display panel 11) having an opening on the display surface side, and a step corresponding to the thickness of the bezel 11A is formed on the outer edge of the opening of the bezel 11A. Exists. The optical transparent adhesive sheet 12 is attached so as to cover the display surface side of the display panel 11 and the bezel 11A, and fills the step. The optical transparent adhesive sheet 12 is required to be flexible to follow the stepped portion and to be thicker than the thickness of the bezel in order to fill the step formed by the thickness of the bezel. Thus, it is preferable that the thickness of the optical transparent adhesive sheet used for bonding with the display panel 11 accommodated in the bezel 11A is 700 μm or more, for example. The optical transparent pressure-sensitive adhesive sheet of the present invention has sufficient optical characteristics and flexibility even when the thickness is 700 μm or more, and is suitably used for bonding to the display panel 11 accommodated in the bezel 11A. it can.

In such a display device, since the optically transparent adhesive sheet of the present invention is used, even if it is used in various environments, the adhesive force of the optically transparent adhesive sheet is not easily lowered, and the optical member is used for a long time. Can be brought into close contact with each other. As a result, since no gap is generated between each optical member and the optical transparent adhesive sheet, it is possible to prevent deterioration in visibility due to an increase in interface reflection or the like. In particular, the optically transparent pressure-sensitive adhesive sheet of the present invention is suitable for a display device or the like incorporated in a car navigation device that requires high reliability because the adhesive strength hardly decreases even at high temperatures and high humidity.

The production method of the optically transparent pressure-sensitive adhesive sheet of the present invention is not particularly limited, and for example, it can be produced by preparing a thermosetting polyurethane composition and then molding the composition while thermosetting it by a conventionally known method. .

As a specific example of the production method, first, a master batch is prepared by adding a predetermined amount of tackifier to a polyol component and dissolving by heating and stirring. Subsequently, the obtained master batch, polyol component, polyisocyanate component and catalyst are mixed and stirred with a mixer or the like to obtain a liquid or gel thermosetting polyurethane composition. At this time, you may add a monoisocyanate component to a masterbatch or a polyol component. Thereafter, the thermosetting polyurethane composition is immediately put into the molding apparatus, and the thermosetting polyurethane composition is cross-linked and cured while being moved while being sandwiched between the protective films, thereby obtaining a sheet integrated with the protective films on both sides. . In addition, in order to improve the handleability of an optical transparent adhesive sheet, it is preferable that the protective film of both surfaces is adjusted so that one peeling strength may become larger than the other peeling strength. Then, the optically transparent adhesive sheet which consists of hardened | cured material of a thermosetting polyurethane composition can be manufactured by making it cross-link in a furnace for a fixed time.

FIG. 2 is a schematic view for explaining an example of a molding apparatus used for producing the optically transparent adhesive sheet of the present invention. In the molding apparatus 20 shown in FIG. 2, first, a polyethylene terephthalate (PET) in which a liquid or gel-like thermosetting polyurethane composition 23 before curing is continuously fed out from a pair of rolls 22 that are spaced apart from each other. Pour into the gap between the protective films 21 made of the metal. Then, while the thermosetting polyurethane composition 23 is held in the gap, the curing reaction (crosslinking reaction) proceeds and the resin is carried into the heating device 24. In the heating device 24, the thermosetting polyurethane composition 23 is thermoset while being held between the pair of protective films 21, and the molding of the optically transparent adhesive sheet 12 made of a cured product of the thermoplastic polyurethane composition is completed. To do.

As a method for producing the optically transparent adhesive sheet of the present invention, after preparing a thermosetting polyurethane composition before curing, various film forming apparatuses such as various coating apparatuses, bar coats, doctor blades and the like are used. There may be. Moreover, you may produce the optical transparent adhesive sheet of this invention using a centrifugal molding method.

EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail about this invention, this invention is not limited only to these Examples.

(Mixed raw materials)
In the following examples and comparative examples, the blending raw materials used for preparing the thermosetting polyurethane resin composition are as follows.
(A) Polyol component polycarbonate polyol (manufactured by Nippon Polyurethane Industry Co., Ltd., L34, number average molecular weight: 500)
(B) Polyisocyanate component HDI-based polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., HC-247)
(C) Tackifier rosin diol type tackifier (Arakawa Chemical Industries, KE-601)
Rosin tack fire (Arakawa Chemical Industries, KE-604)
(D) Catalyst dimethyltin dilaurate (Momentive, Fomrez catalyst UL-28)

The rosin diol tackifier used in the examples (Arakawa Chemical Industries, Ltd., KE-601) has two dehydroabithienic acids (the above chemical formula ( 7) is composed of molecules bonded by a carboxyl group. The rosin diol tackifier used in the examples had a color tone of 400 Hazen or less, an acid value of 1 mgKOH / g or less, a hydroxyl value of 111 to 121 mgKOH / g, and a softening point of 85 to 97 ° C. The rosin tackifier used in the comparative example (Arakawa Chemical Industries, Ltd., KE-604) had a color tone of 300 Hazen or less, an acid value of 230 to 245 mgKOH / g or less, and a softening point of 124 to 134 ° C.

Example 1
First, a solid rosin diol tackifier was added to a polycarbonate polyol whose temperature was adjusted to 115 ° C. and stirred to obtain a master batch in which the rosin tackifier was dissolved in the polycarbonate polyol. At this time, the content of the rosin tackifier in the master batch was adjusted to 30% by weight. Next, 100 parts by weight of polycarbonate polyol, 170.6 parts by weight of HDI polyisocyanate, 42 parts by weight of tackifier masterbatch, and 0.12 parts by weight of catalyst were added to a revolving mixer (Shinky Co., Ltd. Taro ARE-310) was stirred and mixed at 200 rpm for 1 minute to prepare a thermosetting polyurethane resin composition.

Thereafter, the obtained thermosetting polyurethane resin composition was poured into the molding apparatus 20 shown in FIG. 2 and moved in a state of being sandwiched by a protective film (PET film whose surface was subjected to a release treatment) 21. Crosslinking and curing was performed under the conditions of a furnace temperature of 70 ° C. and a furnace time of 10 minutes to obtain a sheet with a protective film. Thereafter, an optically transparent pressure-sensitive adhesive sheet (hereinafter referred to as “optically transparent with a double-sided protective film”) made of a cured product of a thermosetting polyurethane composition, which was subjected to a crosslinking reaction for 1 hour in an oven adjusted to 70 ° C. Also referred to as an “adhesive sheet”.

3 is a cross-sectional view schematically showing the optically transparent adhesive sheet with a double-sided protective film of Example 1. FIG. As shown in FIG. 3, the obtained optically transparent adhesive sheet with a double-sided protective film was a laminate of the protective film 21, the optically transparent adhesive sheet 12 made of a cured product of a thermosetting polyurethane composition, and the protective film 21. . The thickness of the optically transparent adhesive sheet 12 was 300 μm.

(Example 2 and Comparative Examples 1 to 4)
An optically transparent adhesive sheet having a thickness of 300 μm was prepared in the same manner as in Example 1 except that the blending amount of each blending raw material was changed to the amount shown in Table 1.

(Evaluation of optical transparent adhesive sheet)
About the optical transparent adhesive sheet produced by the Example and the comparative example, by the following method, (1) Evaluation of reactivity, (2) Measurement of micro rubber A hardness, (3) Evaluation of adhesive force, and (4 ) Evaluation of optical properties and (5) Evaluation of durability. The results are shown in Table 2.

(1) Evaluation of reactivity In the production process of the optically transparent pressure-sensitive adhesive sheets of Examples and Comparative Examples, when the thermosetting polyurethane resin composition was heated at a furnace temperature of 70 ° C. and a furnace time of 10 minutes, It was confirmed whether the curable polyurethane resin composition was cured.
In the evaluation of reactivity, the case where the thermosetting polyurethane resin composition was cured was evaluated as ◯, and the case where the thermosetting polyurethane resin composition was not cured was evaluated as x.

(2) Measurement of micro rubber A hardness The optically transparent pressure-sensitive adhesive sheet with a double-sided protective film prepared in Examples and Comparative Examples was cut into a length of 75 mm and a width of 25 mm to obtain a test piece. About each test piece, the hardness in normal temperature was measured using the polymer instrument company make, the micro rubber hardness meter MD-1 type A. In this measurement, a push needle having a cylindrical shape with a diameter of 0.16 mm and a height of 0.5 mm was used. One test piece was prepared in each example and comparative example, and measured five times. The median (median value) of the five measured values obtained was taken as the measurement result in each example and comparative example.

(3) Evaluation of adhesive strength A 180 ° peel test was performed by the following method to measure the adhesive strength (N / 25 mm). FIG. 4 is a schematic diagram for explaining a method for evaluating the adhesive strength of the optically transparent adhesive sheets of Examples and Comparative Examples. The optically transparent adhesive sheet with a double-sided protective film produced in the examples and comparative examples was cut into a length of 75 mm and a width of 25 mm to obtain a test piece. After the protective film on one side of the test piece was peeled off, the optical transparent adhesive sheet side was attached to a slide glass having a length of 75 mm × width of 25 mm × thickness of 1.3 mm, held at a pressure of 0.4 MPa for 30 minutes, and optically transparent The adhesive sheet and the slide glass were bonded together. Next, the protective film on the side opposite to the slide glass was peeled off, and as shown in FIG. Film Corporation, Melinex S) 32 was bonded.

Thereafter, as shown in FIG. 4B, the PET sheet 32 is pulled in the 180 ° direction, the optical transparent adhesive sheet 12 is peeled off at the interface with the slide glass 31, and the adhesive strength of the optical transparent adhesive sheet to the slide glass is measured. did. Two test pieces were prepared and measured for each example and comparative example. The average value of the two measured values obtained was taken as the measurement result in each example and comparative example.

(3-1) Adhesive force under normal temperature and normal humidity After the test piece was stored for 12 hours at normal temperature and normal humidity (temperature 23 ° C., humidity 50%), the adhesive strength was measured by the measurement method described above. .

(3-2) Adhesive strength under high temperature and high humidity After the test piece was stored for 24 hours at high temperature and high humidity (temperature 85 ° C., humidity 85%), the adhesive strength was measured by the measurement method shown above. .

(4) Measurement of optical properties The optically transparent adhesive sheet with double-sided protective film produced in the examples and comparative examples was cut into a length of 75 mm and a width of 25 mm to obtain a test piece. After the protective film on one side of this test piece was peeled off, the optical transparent adhesive sheet side was attached to a slide glass having a length of 75 mm × width of 25 mm × thickness of 1.3 mm and held at a pressure of 0.4 MPa for 30 minutes. The adhesive sheet and the slide glass were bonded together. Thereafter, the protective film on the side opposite to the slide glass was peeled off, and the following measurements were performed.

(4-1) Measurement of Haze About the above-mentioned test piece, haze (Haze) was measured by a method based on JIS K 7136 using a turbidimeter (Nippon Denshoku Industries Co., Ltd., NDH2000). . Three test pieces were prepared and measured for each example and comparative example. The average value of the three measured values obtained was taken as the measurement result in each example and comparative example.

(4-2) Total light transmittance About the said test piece, the total light transmittance was measured by the method based on JISK7361-1 using the turbidimeter (the Nippon Denshoku Industries Co., Ltd. make, NDH2000). . Three test pieces were prepared and measured for each example and comparative example. The average value of the three measured values obtained was taken as the measurement result in each example and comparative example.

(5) Durability Evaluation The optically transparent adhesive sheet with double-sided protective film produced in the examples and comparative examples was cut into a length of 75 mm and a width of 25 mm to obtain a test piece. After the protective film on one side of this test piece was peeled off, the optical transparent adhesive sheet side was attached to a slide glass having a length of 75 mm × width of 25 mm × thickness of 1.3 mm and held at a pressure of 0.4 MPa for 30 minutes. The adhesive sheet and the slide glass were bonded together. Thereafter, the protective film opposite to the slide glass was peeled off and stored for 72 hours at high temperature and high humidity (temperature 85 ° C., humidity 85%), and then the state of the optically transparent adhesive sheet was visually observed.
In the evaluation of durability, the case where the shape of the optical transparent pressure-sensitive adhesive sheet did not change was evaluated as ◯, and the case where it changed was determined as ×.

As can be seen from Tables 1 and 2 above, the optically transparent adhesive sheets of Examples 1 and 2 in which a rosin diol-based tackifier is blended with a thermosetting polyurethane resin composition have adhesive strength even at high temperatures and high humidity. Was high (5.5 N / 25 mm or more), and the shape did not change. On the other hand, the optically transparent pressure-sensitive adhesive sheet of Comparative Example 1 in which no tackifier was blended did not have sufficient adhesive strength at high temperatures and high humidity. In addition, the optically transparent adhesive sheets of Comparative Examples 2 to 4 in which a tackifier that is not rosin diol based on the thermosetting polyurethane resin composition is blended, the reactivity of the thermosetting polyurethane resin composition is low, and the furnace temperature It could not be cured under the conditions of 70 ° C. and 10 minutes in the furnace.

DESCRIPTION OF SYMBOLS 10 Display apparatus 11 Display panel 11A Bezel 12 Optical transparent adhesive sheet 13 Touch panel 14 Transparent cover panel 20 Molding apparatus 21 Protective film 22 Roll 23 Thermosetting polyurethane composition 24 Heating apparatus 31 Slide glass 32 PET sheet

Claims (3)

An optically transparent adhesive sheet comprising a cured product of a thermosetting polyurethane composition,
The thermosetting polyurethane composition contains a polyol component, a polyisocyanate component, and a tackifier,
The tackifier includes an rosin diol tackifier, and is an optically transparent adhesive sheet. The thermosetting polyurethane composition has an α ratio (number of moles of OH group derived from polyol component / number of moles of NCO group derived from polyisocyanate component) of 1 or more, and further contains a monoisocyanate component. The optically transparent adhesive sheet according to claim 1. The thickness of the said optically transparent adhesive sheet is 50 micrometers or more and 2000 micrometers or less, The optically transparent adhesive sheet of Claim 1 or 2 characterized by the above-mentioned.

Images