WO2020026955A1 - Adhesive for application to display - Google Patents
Adhesive for application to display Download PDFInfo
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- WO2020026955A1 WO2020026955A1 PCT/JP2019/029315 JP2019029315W WO2020026955A1 WO 2020026955 A1 WO2020026955 A1 WO 2020026955A1 JP 2019029315 W JP2019029315 W JP 2019029315W WO 2020026955 A1 WO2020026955 A1 WO 2020026955A1
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- adhesive
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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
- 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
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
Definitions
- the present invention relates to an adhesive for attaching a display.
- An adhesive for attaching a display, which can adjust contrast and suppress reflection of external light by being attached to a display such as a personal computer monitor, has been proposed.
- a color tone of such an adhesive film neutral gray is usually adopted from the viewpoint of adjusting contrast and suppressing reflection of external light.
- Patent Document 1 discloses an adhesive film for an electronic display in which a pressure-sensitive adhesive layer in which a photopolymerizable compound, a photopolymerization initiator and carbon black are dispersed is provided on one surface of a transparent substrate. Have been.
- an object of the present invention is to provide a display sticking adhesive suitable for a touch screen panel despite being neutral gray.
- the present inventors have conducted intensive studies to solve the above-described problems, and as a result, including a coloring material containing a red pigment, a blue pigment, and a yellow pigment, and after photocuring, a * and C * in a CIE Lab color space display system.
- b * respectively, it found that -3.0 ⁇ a * ⁇ 3.0, -3.0 ⁇ b * satisfy ⁇ 3.0 display sticking adhesive, can solve the above problem, accomplished the present invention I let it.
- the adhesive for pasting a display of the present invention is an adhesive for pasting a display having photocurability, which comprises a coloring material containing a red pigment, a blue pigment, and a yellow pigment, and which is CIE Lab after photocuring.
- a * and b * in the color space display system satisfy ⁇ 3.0 ⁇ a * ⁇ 3.0 and ⁇ 3.0 ⁇ b * ⁇ 3.0, respectively.
- the present embodiment a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail.
- the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the invention.
- neutral gray means that a * and b * in the CIE Lab color space display system are ⁇ 3.0 ⁇ a * ⁇ 3.0 and ⁇ 3.0 ⁇ b * ⁇ 3.0, respectively. It means that it is 0.
- the display bonding adhesive of the present embodiment (hereinafter, also simply referred to as “adhesive”) is a light-curable display bonding adhesive, and is a color containing a red pigment, a blue pigment, and a yellow pigment.
- a * and b * in the CIE Lab color space display system after photo-curing satisfy ⁇ 3.0 ⁇ a * ⁇ 3.0 and ⁇ 3.0 ⁇ b * ⁇ 3.0, respectively. . a * and b * preferably satisfy ⁇ 2.0 ⁇ a * ⁇ 2.0 and ⁇ 2.0 ⁇ b * ⁇ 2.0 from the viewpoint of contrast adjustment, and ⁇ 1.0 ⁇ a *. It is more preferable to satisfy ⁇ 1.0 and ⁇ 1.0 ⁇ b * ⁇ 1.0.
- the adhesive film described in Patent Literature 1 carbon black is used as a pigment for coloring in neutral gray. Therefore, when the adhesive film is applied to a touch screen panel, the function of the touch sensor may be impaired due to the high conductivity of carbon black.
- the adhesive of the present embodiment enables neutral gray coloring by combining a red pigment, a blue pigment, and a yellow pigment. Since the conductivity of such a pigment is extremely low as compared with the conductivity of carbon black, the function of the touch sensor is not impaired even when the adhesive is applied to the touch screen panel. For this reason, the adhesive of the present embodiment can be suitably used for a touch screen panel despite being neutral gray.
- the coloring material contains a red pigment, a blue pigment, and a yellow pigment.
- a dye as a coloring material.
- the obtained adhesive may not have sufficient environmental resistance (for example, heat resistance) and weather resistance.
- the obtained adhesive can sufficiently improve environmental resistance and weather resistance.
- the coloring material may contain other pigments as long as the effects of the present invention are not impaired.
- red pigment examples include red iron oxide, cadmium red, molybdenum red, naphthol AS-based azo red, anthanthrone, anthraquinone red, perylene maroon, quinacridone-based red pigment, diketopyrrolopyrrole, watching red, permanent red, and the like.
- red pigments are used alone or in combination of two or more.
- the red pigment is preferably anthraquinone red. By using such a red pigment, the adhesive tends to be more excellent in environmental resistance and weather resistance.
- the blue pigment examples include cobalt blue, Prussian blue, phthalocyanine blue, and sllen blue. These pigments are used alone or in combination of two or more. Among these, the blue pigment is preferably phthalocyanine blue. By using such a blue pigment, the adhesive tends to be more excellent in environmental resistance and weather resistance.
- the yellow pigment for example, yellow iron oxide, titanium yellow, chrome yellow, chromium oxide, monoazo yellow, condensed azo yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent Yellow and the like. These pigments are used alone or in combination of two or more. Among these, the yellow pigment is preferably isoindolinone. By using such a yellow pigment, the adhesive tends to be more excellent in environmental resistance and weather resistance.
- the average particle size of each pigment is preferably from 10 to 200 nm, more preferably from 50 to 180 nm, even more preferably from 70 to 175 nm. When the average particle diameter of each pigment is within the above range, the visibility tends to be further excellent while maintaining neutral gray.
- the average particle size of each pigment refers to a value measured using a “laser diffraction particle size distribution analyzer SALD-200” manufactured by Shimadzu Corporation. To the sample, 50 g of pure water and 5 g of a pigment to be measured are added to a glass beaker, stirred using a spatula, and then subjected to a dispersion treatment for 10 minutes by an ultrasonic cleaner.
- the pigment solution subjected to the dispersion treatment is added drop by drop to the sampler section of the apparatus with a dropper, and it is waited for the absorbance to stabilize until it can be measured. When the absorbance becomes stable, the measurement is performed.
- the particle size distribution is calculated from the data of the light intensity distribution of the diffraction / scattered light by the particles detected by the sensor.
- the average particle size is determined by multiplying the measured particle size by the relative particle amount (% difference) and dividing by the total relative particle amount (100%).
- the average particle diameter is the average diameter of the particles.
- “%” here indicates volume%.
- the content of each pigment is not particularly limited as long as neutral gray can be achieved, but the content of the red pigment is 37 to 41% by mass and the content of the blue pigment is 25 to 19% by mass based on the entire coloring material. It is preferable that the content of the yellow pigment is 37 to 41% by mass, the content of the red pigment is 38 to 40% by mass, the content of the blue pigment is 26 to 18% by mass, More preferably, the content is 38 to 40% by mass.
- each value of a * and b * in the CIE Lab color space display system tends to be able to approach 0.
- secondary particles of a coloring material having a size of 5.0 ⁇ m or more substantially exist in an optical microscope image per 5 mm 2.
- the haze of the adhesive can be reduced, and the transmittance tends to be excellent.
- the term "substantially free” does not mean that no present at all, meaning that no such an extent that affects the haze of the adhesive, preferably per 5 mm 2
- the optical microscope image shows that the secondary particles cannot be found when observed at a magnification of 1500 times.
- the adhesive of the present embodiment may contain a UV-curable prepolymer in order to have photocurability.
- the UV-curable prepolymer include urethane (meth) acrylate having a urethane structure in a main chain and a (meth) acryl group in a side chain.
- the urethane (meth) acrylate include urethane (meth) acrylate having a polycarbonate skeleton, urethane (meth) acrylate having a polyether skeleton, and urethane (meth) acrylate having a polyester skeleton.
- urethane (meth) acrylate having a polycarbonate skeleton is preferable as the UV-curable prepolymer from the viewpoint of non-yellowing.
- the urethane (meth) acrylate having a polycarbonate skeleton refers to a prepolymer having a polycarbonate structure and a urethane structure in a main chain and having a (meth) acryl group in a side chain.
- the urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting polycarbonate diol, diisocyanate, and carboxylic acid diol, and then reacting glycidyl (meth) acrylate.
- the weight average molecular weight of the polycarbonate diol is preferably from 170 to 1,000, more preferably from 300 to 700, and still more preferably from 400 to 600 in terms of polystyrene by gel permeation chromatography (GPC).
- the diisocyanate is not particularly limited.
- Aromatic isocyanates such as 1,5-naphthalene diisocyanate (NDI); hexamethylene isocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate
- Aliphatic polyisocyanates such as Tomechiru (NBDI
- the carboxylic acid diol is not particularly limited, and includes, for example, dimethylolbutanoic acid, dimethylolpropionic acid, and the like.
- a urethane (meth) acrylate having a polyether skeleton refers to a prepolymer having a polyether structure and a urethane structure in a main chain, and having a (meth) acryl group in a side chain.
- the urethane (meth) acrylate having a polyester skeleton refers to a prepolymer having a polyester structure and a urethane structure in a main chain and having a (meth) acryl group in a side chain.
- prepolymers can be obtained by the same method as for the urethane (meth) acrylate having a polycarbonate skeleton except that a polyether diol and a polyester diol are used instead of the polycarbonate diol, respectively.
- the preferable weight average molecular weight of the polyether diol and the polyester diol is the same as the preferable weight average molecular weight of the above-mentioned polycarbonate diol.
- the weight-average molecular weight of the UV-curable prepolymer is preferably from 10,000 to 100,000, more preferably from 30,000 to 70,000, even more preferably from 40,000 to 60,000 in terms of polystyrene by GPC. 000.
- the weight average molecular weight is in the above range, the film formability and the curability tend to be more excellent.
- the double bond equivalent of the UV-curable prepolymer is preferably from 1,000 to 5,000 g / eq, more preferably from 1,500 to 2,500 g / eq, and still more preferably from 1,800 to 2,500 g / eq. It is 200 g / eq.
- the double bond equivalent was calculated by dividing the solid content mass (g) of the carboxyl group-containing (meth) acrylate by the number of moles (g / mol) of the compound having an oxirane ring and an ethylenically unsaturated bond. Value.
- the content of the coloring material may be about 1 to 10 parts by mass with respect to 100 parts by mass of the UV-curable prepolymer.
- the content of the coloring material is a part by mass in a slurry state.
- UV curable monomer The adhesive of the present embodiment may contain a UV curable monomer.
- UV-curable monomers include (meth) acrylic monomers. These (meth) acrylic monomers are used alone or in combination of two or more. Among them, a hydroxyl group-containing (meth) acrylic monomer is preferable from the viewpoint of suppressing an increase in haze under a high temperature and high humidity environment. Examples of the hydroxyl group-containing (meth) acrylic monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyethyl (meth) acrylate.
- Hydroxyoctyl (meth) acrylate caprolactone-modified 2-hydroxyethyl (meth) acrylate, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, 2-acryloyloxyethyl 2-hydroxyethyl phthalate, 2-hydroxypropyl (meth) ) Acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2,2-dimethyl2-hydroxyethyl (meth) acrylate And the like.
- the content of the UV curable monomer may be about 20 to 50 parts by mass based on 100 parts by mass of the UV curable prepolymer.
- the adhesive of the present embodiment may contain a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited, for example, any photopolymerization initiator such as an acylphosphine oxide-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an intramolecular hydrogen abstraction type photopolymerization initiator. Used. Among these, from the viewpoint of reactivity and uniformity of curing, the photopolymerization initiator is preferably an acylphosphine oxide-based photopolymerization initiator.
- the photopolymerization initiator examples include 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethan-1-one, and phenylglyoxylic acid methyl ester.
- 2,4,6-trimethylbenzoylphenylphosphine oxide is preferred from the viewpoint of high radical generation efficiency and deep part curability.
- the content of the photopolymerization initiator may be about 0.5 to 5.0 parts by mass based on 100 parts by mass of the UV-curable prepolymer.
- the adhesive of the present embodiment may contain a silane coupling agent.
- a silane coupling agent for example, any silane coupling agent such as a monomer type silane coupling agent, an alkoxy oligomer type silane coupling agent, and a polyfunctional type silane coupling agent can be used.
- the silane coupling agent is preferably a silane coupling agent having a (meth) acrylic group ((meth) acrylic silane coupling agent), 3-acryloxypropyltrimethoxysilane is more preferred.
- the content of the silane coupling agent may be about 0.1 to 10 parts by mass with respect to 100 parts by mass of the UV-curable prepolymer.
- the adhesive of the present embodiment includes various fillers such as silica, alumina, and hydrated alumina, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, leveling agents, defoamers, coloring pigments, organic solvents, and the like. , And may include additives that are usually added to the adhesive.
- the haze after photocuring is preferably 5.0% or less, more preferably 4.0% or less, and even more preferably 3.0% or less.
- the adhesive tends to be more excellent in transparency.
- haze is determined by a method described in Examples described later.
- the transmittance after photocuring is preferably 40 to 60%, more preferably 45 to 55%.
- the adhesive tends to be more excellent in visibility while maintaining neutral gray.
- the transmittance is determined by the method described in Examples described later.
- the hue change ⁇ E after photo-curing is preferably 1.0 or less, more preferably 0.8 or less, and even more preferably 0.5 or less.
- ⁇ E is within the above range, the adhesive tends to be more excellent in environmental resistance. ⁇ E is determined by a method described in Examples described later.
- the adhesive of this embodiment is used for attaching a display.
- the display include an electronic display such as a liquid crystal display, a plasma display, a CRT, electroluminescence, and a touch screen panel.
- the touch screen panel is preferable because the function of the touch sensor is less likely to be impaired.
- the adhesive of the present embodiment can effectively suppress the reflection of external light, the electronic display is preferably for a vehicle.
- the adhesive sheet of the present embodiment includes the adhesive of the present embodiment.
- a first base material, an adhesive layer, and a second base material are laminated in this order, and the adhesive layer is formed of the adhesive of the present embodiment.
- the first base material and the second base material may be, for example, a known base material having releasability (for example, a PET film or the like).
- the thickness of the adhesive sheet may be, for example, about 10 to 250 ⁇ m.
- the obtained UV-curable prepolymer (A) had a weight average molecular weight of 50,000, a solid content concentration of 50% by mass, a double bond equivalent of 2,000 g / eq, and a Tg of 5 ° C.
- Tg can be determined from the peak value of TAN ⁇ (tensile loss modulus E ′′ / tensile storage modulus E ′) using dynamic viscoelasticity measurement (DMA: Dynamic Mechanical Analysis). For example, it can be measured using a test piece having a width of 5 mm, a length of 50 mm, and a thickness of 0.1 ⁇ m.
- the double bond equivalent is represented by the mass of the polymer per 1 mol of the double bond, and is calculated by the following formula.
- Double bond equivalent (g / eq) mass (g) of (meth) acrylic polymer / molar amount of double bond (mol) of (meth) acrylic polymer
- x 10 ⁇ Vf ⁇ 56.1 / (Wp ⁇ I) ( ⁇ ) (In the formula ( ⁇ ), x represents an acid value (mg KOH / g), Vf represents a titer (mL) of a 0.1 N KOH aqueous solution, Wp represents a measured mass (g) of the resin solution, I indicates the measured ratio of nonvolatile components in the resin solution (% by mass).)
- Weight average molecular weight measurement method Here, the weight average molecular weight was measured by GPC using standard polystyrene having an average molecular weight of about 500 to about 1,000,000.
- Equipment Tosoh HLC-8120GPC
- TSKgel SuperM M and two TSKgel SuperH-2000 are connected in series. A total of three columns
- Detector Differential refractive index detector Measurement temperature: 40 ° C
- Examples 1 to 16 and Comparative Examples 1 to 4 The components shown in Tables 1 to 4 were added in the amounts shown in Tables 1 to 4 and stirred to obtain an adhesive (resin composition). The viscosity was adjusted while adding about 100 parts by mass of methyl ethyl ketone as a solvent during the addition. In addition, the number in Table 1 shows solid content. In the table, “4-HBA” indicates 4-hydroxybutyl acrylate, and “TPO” indicates 2,4,6-trimethylbenzoylphenylphosphine oxide.
- the obtained adhesive was applied on release PET 50 ⁇ m so that the thickness after drying was 25 ⁇ m, and dried at 130 ° C. for 5 minutes. Then, release PET 38 ⁇ m was placed on the opposite surface to obtain an adhesive sheet. . Each physical property was evaluated using the obtained adhesive sheet. The thickness of the adhesive was determined by measuring the thickness of the entire adhesive sheet using VA-50A manufactured by Mitutoyo, and subtracting the thickness of the release PET therefrom.
- the one-sided release PET of the obtained adhesive sheet was peeled off, and bonded to a “TAC film” made by Fuji Film with a thickness of 80 ⁇ m (40 mm square) by roll lamination. Roll lamination was performed at a temperature of 25 to 50 ° C., a pressure of 0.1 to 0.4 MPa, and a speed of 0.5 to 1.0 m / min.
- a polycarbonate film having a thickness of 1.0 mm (40 mm square) manufactured by Mitsubishi Gas Chemical was bonded by vacuum lamination.
- Transmissivity evaluation The same evaluation sample as that prepared in the section [Hue evaluation] was used. It was measured according to JIS K7136. ⁇ : The transmittance was within 50 ⁇ 5%. X: The transmittance was less than 45% or more than 55%.
- the conditions are black panel temperature 63 ⁇ 3 ° C, water injection conditions (pressure 0.08 to 0.13MPa, water amount 660 ⁇ 60ml / min, injection time 12 minutes / 60 minutes, water temperature 16 ⁇ 5 ° C), relative humidity 50 ⁇ 5%, sample surface irradiance 60 ⁇ 3 W / m 2 (300 to 400 nm), 180 ⁇ 3 W / m 2 (300 to 400 nm).
- ⁇ E [( ⁇ L * ) 2 + ( ⁇ a * ) 2 + ( ⁇ b * ) 2 ] 1/2 ⁇ ⁇ ⁇ ⁇ ⁇ E 1.0 ⁇ ⁇ ⁇ ⁇ 1.0 ⁇ E
- Tables 1 to 4 show the evaluation results of each physical property.
- the adhesive of the present invention has industrial applicability as an adhesive for attaching a display such as a touch screen panel.
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Abstract
The adhesive for application to displays of the present invention has photocurability, and contains a colorant comprising a red pigment, a blue pigment, and a yellow pigment and has, after photocuring, values of a* and b* in the CIE Lab color space system which satisfy -3.0≤a*≤3.0 and -3.0≤b*≤3.0.
Description
本発明は、ディスプレイ貼付用接着剤に関する。
The present invention relates to an adhesive for attaching a display.
パソコンモニター等のディスプレイに貼付けることにより、コントラストを調整したり、外光反射を抑制したりすることができるディスプレイ貼付用接着剤（接着フィルム）が提案されている。このような接着フィルムの色調としては、コントラストの調整及び外光反射の抑制の観点から、通常、ニュートラルグレイが採用されている。
(4) An adhesive (adhesive film) for attaching a display, which can adjust contrast and suppress reflection of external light by being attached to a display such as a personal computer monitor, has been proposed. As a color tone of such an adhesive film, neutral gray is usually adopted from the viewpoint of adjusting contrast and suppressing reflection of external light.
このような接着フィルムとして、特許文献１には、透明基材の一面に、光重合性化合物、光重合開始剤及びカーボンブラックを分散させた粘着剤層を設けた電子ディスプレイ用貼着フィルムが開示されている。
As such an adhesive film, Patent Document 1 discloses an adhesive film for an electronic display in which a pressure-sensitive adhesive layer in which a photopolymerizable compound, a photopolymerization initiator and carbon black are dispersed is provided on one surface of a transparent substrate. Have been.
近年、様々なディスプレイにタッチセンサを設けたタッチスクリーンパネルが導入されている。特許文献１に記載の貼着フィルムをタッチスクリーンパネルに適用した場合、貼着フィルムに含まれるカーボンブラックが高い導電性を有することに起因して、タッチセンサの機能を損なう虞がある。
In recent years, touch screen panels provided with touch sensors on various displays have been introduced. When the sticking film described in Patent Document 1 is applied to a touch screen panel, the function of the touch sensor may be impaired due to the high conductivity of the carbon black contained in the sticking film.
そこで、本発明の目的は、ニュートラルグレイであるにもかかわらず、タッチスクリーンパネルに好適なディスプレイ貼付用接着剤を提供することにある。
Therefore, an object of the present invention is to provide a display sticking adhesive suitable for a touch screen panel despite being neutral gray.
本発明者らは、上記課題を解決するために鋭意検討した結果、赤色顔料、青色顔料、及び黄色顔料を含有する色材を含み、光硬化後における、ＣＩＥ Ｌａｂ色空間表示系におけるａ＊及びｂ＊が、それぞれ、－３．０≦ａ＊≦３．０、－３．０≦ｂ＊≦３．０を満たすディスプレイ貼付用接着剤が、上記課題を解決できることを見出し、本発明を完成させた。
Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-described problems, and as a result, including a coloring material containing a red pigment, a blue pigment, and a yellow pigment, and after photocuring, a * and C * in a CIE Lab color space display system. b *, respectively, it found that -3.0 ≦ a * ≦ 3.0, -3.0 ≦ b * satisfy ≦ 3.0 display sticking adhesive, can solve the above problem, accomplished the present invention I let it.
すなわち、本発明のディスプレイ貼付用接着剤は、光硬化性を有するディスプレイ貼付用接着剤であって、赤色顔料、青色顔料、及び黄色顔料を含有する色材を含み、光硬化後における、ＣＩＥ Ｌａｂ色空間表示系におけるａ＊及びｂ＊が、それぞれ、－３．０≦ａ＊≦３．０、－３．０≦ｂ＊≦３．０を満たす。
That is, the adhesive for pasting a display of the present invention is an adhesive for pasting a display having photocurability, which comprises a coloring material containing a red pigment, a blue pigment, and a yellow pigment, and which is CIE Lab after photocuring. A * and b * in the color space display system satisfy −3.0 ≦ a * ≦ 3.0 and −3.0 ≦ b * ≦ 3.0, respectively.
本発明によれば、ニュートラルグレイであるにもかかわらず、タッチスクリーンパネルに好適なディスプレイ貼付用接着剤を提供可能である。
According to the present invention, it is possible to provide a display bonding adhesive suitable for a touch screen panel despite being neutral gray.
以下、本発明を実施するための形態（以下、「本実施形態」という。）について詳細に記載する。なお、本発明は以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。
Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the invention.
本明細書において、「ニュートラルグレイ」とは、ＣＩＥ Ｌａｂ色空間表示系におけるａ＊及びｂ＊が、それぞれ、－３．０≦ａ＊≦３．０、－３．０≦ｂ＊≦３．０であることをいう。
In this specification, “neutral gray” means that a * and b * in the CIE Lab color space display system are −3.0 ≦ a * ≦ 3.0 and −3.0 ≦ b * ≦ 3.0, respectively. It means that it is 0.
〔ディスプレイ貼付用接着剤〕
本実施形態のディスプレイ貼付用接着剤（以下、単に「接着剤」ともいう。）は、光硬化性を有するディスプレイ貼付用接着剤であって、赤色顔料、青色顔料、及び黄色顔料を含有する色材を含み、光硬化後における、ＣＩＥ Ｌａｂ色空間表示系におけるａ＊及びｂ＊が、それぞれ、－３．０≦ａ＊≦３．０、－３．０≦ｂ＊≦３．０を満たす。ａ＊及びｂ＊は、コントラストの調整の観点から、－２．０≦ａ＊≦２．０、－２．０≦ｂ＊≦２．０を満たすことが好ましく、－１．０≦ａ＊≦１．０、－１．０≦ｂ＊≦１．０を満たすことがより好ましい。 [Display adhesive]
The display bonding adhesive of the present embodiment (hereinafter, also simply referred to as “adhesive”) is a light-curable display bonding adhesive, and is a color containing a red pigment, a blue pigment, and a yellow pigment. A * and b * in the CIE Lab color space display system after photo-curing satisfy −3.0 ≦ a * ≦ 3.0 and −3.0 ≦ b * ≦ 3.0, respectively. . a * and b * preferably satisfy −2.0 ≦ a * ≦ 2.0 and −2.0 ≦ b * ≦ 2.0 from the viewpoint of contrast adjustment, and −1.0 ≦ a *. It is more preferable to satisfy ≦ 1.0 and −1.0 ≦ b * ≦ 1.0.
本実施形態のディスプレイ貼付用接着剤（以下、単に「接着剤」ともいう。）は、光硬化性を有するディスプレイ貼付用接着剤であって、赤色顔料、青色顔料、及び黄色顔料を含有する色材を含み、光硬化後における、ＣＩＥ Ｌａｂ色空間表示系におけるａ＊及びｂ＊が、それぞれ、－３．０≦ａ＊≦３．０、－３．０≦ｂ＊≦３．０を満たす。ａ＊及びｂ＊は、コントラストの調整の観点から、－２．０≦ａ＊≦２．０、－２．０≦ｂ＊≦２．０を満たすことが好ましく、－１．０≦ａ＊≦１．０、－１．０≦ｂ＊≦１．０を満たすことがより好ましい。 [Display adhesive]
The display bonding adhesive of the present embodiment (hereinafter, also simply referred to as “adhesive”) is a light-curable display bonding adhesive, and is a color containing a red pigment, a blue pigment, and a yellow pigment. A * and b * in the CIE Lab color space display system after photo-curing satisfy −3.0 ≦ a * ≦ 3.0 and −3.0 ≦ b * ≦ 3.0, respectively. . a * and b * preferably satisfy −2.0 ≦ a * ≦ 2.0 and −2.0 ≦ b * ≦ 2.0 from the viewpoint of contrast adjustment, and −1.0 ≦ a *. It is more preferable to satisfy ≦ 1.0 and −1.0 ≦ b * ≦ 1.0.
特許文献１に記載された貼着フィルムでは、ニュートラルグレイに着色するために、顔料としてカーボンブラックを用いている。このため、上記貼着フィルムをタッチスクリーンパネルに適用した場合、カーボンブラックが高い導電性を有することに起因して、タッチセンサの機能を損なう虞がある。これに対し、本実施形態の接着剤は、赤色顔料、青色顔料、及び黄色顔料を組み合わせることにより、ニュートラルグレイの着色を可能としている。このような顔料の導電性は、カーボンブラックの導電性と比べると極めて低いため、接着剤をタッチスクリーンパネルに適用しても、タッチセンサの機能を損なうことがない。このため、本実施形態の接着剤は、ニュートラルグレイであるにもかかわらず、タッチスクリーンパネルに好適に用いることができる。
貼 In the adhesive film described in Patent Literature 1, carbon black is used as a pigment for coloring in neutral gray. Therefore, when the adhesive film is applied to a touch screen panel, the function of the touch sensor may be impaired due to the high conductivity of carbon black. On the other hand, the adhesive of the present embodiment enables neutral gray coloring by combining a red pigment, a blue pigment, and a yellow pigment. Since the conductivity of such a pigment is extremely low as compared with the conductivity of carbon black, the function of the touch sensor is not impaired even when the adhesive is applied to the touch screen panel. For this reason, the adhesive of the present embodiment can be suitably used for a touch screen panel despite being neutral gray.
〔色材〕
色材は、赤色顔料、青色顔料及び黄色顔料を含有する。ここで、色材として染料を用いることも考えられるが、染料を用いると、得られる接着剤の耐環境性（例えば、耐熱性等）、耐候性が十分に得られない虞がある。これに対し、本実施形態では色材として顔料を用いることにより、得られる接着剤は、耐環境性及び耐候性を十分に向上できる。なお、色材は、本発明の作用効果を阻害しない範囲においてその他の顔料を含有してもよい。 (Color material)
The coloring material contains a red pigment, a blue pigment, and a yellow pigment. Here, it is conceivable to use a dye as a coloring material. However, if a dye is used, there is a possibility that the obtained adhesive may not have sufficient environmental resistance (for example, heat resistance) and weather resistance. On the other hand, in the present embodiment, by using a pigment as a coloring material, the obtained adhesive can sufficiently improve environmental resistance and weather resistance. The coloring material may contain other pigments as long as the effects of the present invention are not impaired.
色材は、赤色顔料、青色顔料及び黄色顔料を含有する。ここで、色材として染料を用いることも考えられるが、染料を用いると、得られる接着剤の耐環境性（例えば、耐熱性等）、耐候性が十分に得られない虞がある。これに対し、本実施形態では色材として顔料を用いることにより、得られる接着剤は、耐環境性及び耐候性を十分に向上できる。なお、色材は、本発明の作用効果を阻害しない範囲においてその他の顔料を含有してもよい。 (Color material)
The coloring material contains a red pigment, a blue pigment, and a yellow pigment. Here, it is conceivable to use a dye as a coloring material. However, if a dye is used, there is a possibility that the obtained adhesive may not have sufficient environmental resistance (for example, heat resistance) and weather resistance. On the other hand, in the present embodiment, by using a pigment as a coloring material, the obtained adhesive can sufficiently improve environmental resistance and weather resistance. The coloring material may contain other pigments as long as the effects of the present invention are not impaired.
赤色顔料としては、例えば、赤色酸化鉄、カドミウムレッド、モリブデンレッド、ナフトールＡＳ系アゾレッド、アンサンスロン、アンスラキノンレッド、ペリレンマルーン、キナクリドン系赤顔料、ジケトピロロピロール、ウォッチングレッド、パーマネントレッド等が挙げられる。これらの顔料は、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、赤色顔料は、アンスラキノンレッドであることが好ましい。このような赤色顔料を用いることにより、接着剤は、耐環境性及び耐候性に一層優れる傾向にある。
Examples of the red pigment include red iron oxide, cadmium red, molybdenum red, naphthol AS-based azo red, anthanthrone, anthraquinone red, perylene maroon, quinacridone-based red pigment, diketopyrrolopyrrole, watching red, permanent red, and the like. Can be These pigments are used alone or in combination of two or more. Among these, the red pigment is preferably anthraquinone red. By using such a red pigment, the adhesive tends to be more excellent in environmental resistance and weather resistance.
青色顔料としては、例えば、コバルトブルー、プルシアンブルー、フタロシアニンブルー、スレンブルー等が挙げられる。これらの顔料は、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、青色顔料は、フタロシアニンブルーであることが好ましい。このような青色顔料を用いることにより、接着剤は、耐環境性及び耐候性に一層優れる傾向にある。
Examples of the blue pigment include cobalt blue, Prussian blue, phthalocyanine blue, and sllen blue. These pigments are used alone or in combination of two or more. Among these, the blue pigment is preferably phthalocyanine blue. By using such a blue pigment, the adhesive tends to be more excellent in environmental resistance and weather resistance.
黄色顔料としては、例えば、黄色酸化鉄、チタンイエロー、クロムエロー、酸化クロム、モノアゾイエロー、縮合アゾイエロー、アゾメチンイエロー、ビスマスバナデート、ベンズイミダゾロン、イソインドリノン、イソインドリン、キノフタロン、ベンジジンイエロー、パーマネントイエロー等が挙げられる。これらの顔料は、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、黄色顔料は、イソインドリノンであることが好ましい。このような黄色顔料を用いることにより、接着剤は、耐環境性及び耐候性に一層優れる傾向にある。
As the yellow pigment, for example, yellow iron oxide, titanium yellow, chrome yellow, chromium oxide, monoazo yellow, condensed azo yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent Yellow and the like. These pigments are used alone or in combination of two or more. Among these, the yellow pigment is preferably isoindolinone. By using such a yellow pigment, the adhesive tends to be more excellent in environmental resistance and weather resistance.
色材として、このような顔料を用いることにより、ＣＩＥ Ｌａｂ色空間表示系におけるａ＊及びｂ＊の各値を０に近づけることができる傾向にある。
By using such a pigment as a coloring material, there is a tendency that each value of a * and b * in the CIE Lab color space display system can be made closer to 0.
各顔料の平均粒径は、１０～２００ｎｍであることが好ましく、５０～１８０ｎｍであることがより好ましく、７０～１７５ｎｍであることが更に好ましい。各顔料の平均粒径が上記範囲内であることにより、ニュートラルグレイを維持しつつ、視認性に一層優れる傾向にある。各顔料の平均粒径は、島津製作所製「レーザー回折式粒度分布測定装置ＳＡＬＤ－２００」を用いて測定した値をいう。試料は、ガラスビーカーに５０ｃｃの純水と測定する顔料を５ｇ添加して、スパチュラを用いて撹拌し、その後超音波洗浄機で１０分間、分散処理を行う。分散処理を行った顔料の溶液をスポイトで装置のサンプラ部に一滴ずつ添加して、吸光度が測定可能になるまで安定するのを待ち、吸光度が安定になった時点で測定を行う。レーザー回折式粒度分布測定装置では、センサーで検出した粒子による回折／散乱光の光強度分布のデータから粒度分布を計算する。平均粒子径は測定される粒子径の値に相対粒子量（差分％）を乗じて、相対粒子量の合計（１００％）で割って求める。平均粒子径は、粒子の平均直径である。また、ここでの「％」は体積％を示す。
平均 The average particle size of each pigment is preferably from 10 to 200 nm, more preferably from 50 to 180 nm, even more preferably from 70 to 175 nm. When the average particle diameter of each pigment is within the above range, the visibility tends to be further excellent while maintaining neutral gray. The average particle size of each pigment refers to a value measured using a “laser diffraction particle size distribution analyzer SALD-200” manufactured by Shimadzu Corporation. To the sample, 50 g of pure water and 5 g of a pigment to be measured are added to a glass beaker, stirred using a spatula, and then subjected to a dispersion treatment for 10 minutes by an ultrasonic cleaner. The pigment solution subjected to the dispersion treatment is added drop by drop to the sampler section of the apparatus with a dropper, and it is waited for the absorbance to stabilize until it can be measured. When the absorbance becomes stable, the measurement is performed. In the laser diffraction type particle size distribution measuring device, the particle size distribution is calculated from the data of the light intensity distribution of the diffraction / scattered light by the particles detected by the sensor. The average particle size is determined by multiplying the measured particle size by the relative particle amount (% difference) and dividing by the total relative particle amount (100%). The average particle diameter is the average diameter of the particles. In addition, “%” here indicates volume%.
各顔料の含有量は、ニュートラルグレイを達成できる限り特に限定されないが、色材全体に対し、赤色顔料の含有量が３７～４１質量％であり、青色顔料の含有量が２５～１９質量％であり、黄色顔料の含有量が３７～４１質量％であることが好ましく、赤色顔料の含有量が３８～４０質量％であり、青色顔料の含有量が２６～１８質量％であり、黄色顔料の含有量が３８～４０質量％であることがより好ましい。各顔料の含有量が上記範囲内にあることにより、ＣＩＥ Ｌａｂ色空間表示系におけるａ＊及びｂ＊の各値を０に近づけることができる傾向にある。
The content of each pigment is not particularly limited as long as neutral gray can be achieved, but the content of the red pigment is 37 to 41% by mass and the content of the blue pigment is 25 to 19% by mass based on the entire coloring material. It is preferable that the content of the yellow pigment is 37 to 41% by mass, the content of the red pigment is 38 to 40% by mass, the content of the blue pigment is 26 to 18% by mass, More preferably, the content is 38 to 40% by mass. When the content of each pigment is within the above range, each value of a * and b * in the CIE Lab color space display system tends to be able to approach 0.
本実施形態の接着剤において、５ｍｍ２当たりの光学顕微鏡像において、５．０μｍ以上（好ましくは４．５μｍ以上、より好ましくは４．３μｍ以上）である色材の二次粒子が実質的に存在しないことが好ましい。これにより、接着剤のヘイズを小さくでき、透過性に優れる傾向にある。ここでいう「実質的に存在しない」とは、全く存在していないことを意味するのではなく、接着剤のヘイズに影響を与える程度に存在しないことを意味し、好ましくは、５ｍｍ２当たりの光学顕微鏡像において、倍率１５００倍で観察した場合に、前記二次粒子を発見できないことを示す。
In the adhesive of the present embodiment, secondary particles of a coloring material having a size of 5.0 μm or more (preferably 4.5 μm or more, more preferably 4.3 μm or more) substantially exist in an optical microscope image per 5 mm 2. Preferably not. Thereby, the haze of the adhesive can be reduced, and the transmittance tends to be excellent. The term "substantially free" does not mean that no present at all, meaning that no such an extent that affects the haze of the adhesive, preferably per 5 mm 2 The optical microscope image shows that the secondary particles cannot be found when observed at a magnification of 1500 times.
〔ＵＶ硬化型プレポリマー〕
本実施形態の接着剤は、光硬化性を有するためにＵＶ硬化型プレポリマーを含有してもよい。ＵＶ硬化型プレポリマーとしては、例えば、ウレタン構造を主鎖に、（メタ）アクリル基を側鎖に含むウレタン（メタ）アクリレートが挙げられる。ウレタン（メタ）アクリレートとしては、例えば、ポリカーボネート骨格を有するウレタン（メタ）アクリレート、ポリエーテル骨格を有するウレタン（メタ）アクリレート、ポリエステル骨格を有するウレタン（メタ）アクリレート等が挙げられる。これらの中でも、ＵＶ硬化型プレポリマーは、無黄変性の観点から、ポリカーボネート骨格を有するウレタン（メタ）アクリレートが好ましい。 [UV curable prepolymer]
The adhesive of the present embodiment may contain a UV-curable prepolymer in order to have photocurability. Examples of the UV-curable prepolymer include urethane (meth) acrylate having a urethane structure in a main chain and a (meth) acryl group in a side chain. Examples of the urethane (meth) acrylate include urethane (meth) acrylate having a polycarbonate skeleton, urethane (meth) acrylate having a polyether skeleton, and urethane (meth) acrylate having a polyester skeleton. Among these, urethane (meth) acrylate having a polycarbonate skeleton is preferable as the UV-curable prepolymer from the viewpoint of non-yellowing.
本実施形態の接着剤は、光硬化性を有するためにＵＶ硬化型プレポリマーを含有してもよい。ＵＶ硬化型プレポリマーとしては、例えば、ウレタン構造を主鎖に、（メタ）アクリル基を側鎖に含むウレタン（メタ）アクリレートが挙げられる。ウレタン（メタ）アクリレートとしては、例えば、ポリカーボネート骨格を有するウレタン（メタ）アクリレート、ポリエーテル骨格を有するウレタン（メタ）アクリレート、ポリエステル骨格を有するウレタン（メタ）アクリレート等が挙げられる。これらの中でも、ＵＶ硬化型プレポリマーは、無黄変性の観点から、ポリカーボネート骨格を有するウレタン（メタ）アクリレートが好ましい。 [UV curable prepolymer]
The adhesive of the present embodiment may contain a UV-curable prepolymer in order to have photocurability. Examples of the UV-curable prepolymer include urethane (meth) acrylate having a urethane structure in a main chain and a (meth) acryl group in a side chain. Examples of the urethane (meth) acrylate include urethane (meth) acrylate having a polycarbonate skeleton, urethane (meth) acrylate having a polyether skeleton, and urethane (meth) acrylate having a polyester skeleton. Among these, urethane (meth) acrylate having a polycarbonate skeleton is preferable as the UV-curable prepolymer from the viewpoint of non-yellowing.
ポリカーボネート骨格を有するウレタン（メタ）アクリレートとは、主鎖にポリカーボネート構造とウレタン構造を有し、側鎖に（メタ）アクリル基を有するプレポリマーのことをいう。ポリカーボネート骨格を有するウレタン（メタ）アクリレートは、例えば、ポリカーボネートジオールとジイソシアネートとカルボン酸ジオールとを反応させた後、グリシジル（メタ）アクリレートを反応させることにより得ることができる。
(4) The urethane (meth) acrylate having a polycarbonate skeleton refers to a prepolymer having a polycarbonate structure and a urethane structure in a main chain and having a (meth) acryl group in a side chain. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting polycarbonate diol, diisocyanate, and carboxylic acid diol, and then reacting glycidyl (meth) acrylate.
ポリカーボネートジオールの重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算で好ましくは１７０～１，０００であり、より好ましくは３００～７００であり、さらに好ましくは４００～６００である。
The weight average molecular weight of the polycarbonate diol is preferably from 170 to 1,000, more preferably from 300 to 700, and still more preferably from 400 to 600 in terms of polystyrene by gel permeation chromatography (GPC).
ジイソシアネートとしては、特に限定されず、例えば、２，４―トリレンジイソシアネート（２，４－ＴＤＩ）、２，６－トリレンジイソシアネート（２，６－ＴＤＩ）、４，４’－ジフェニルメタンジイソシアネート（４，４’―ＭＤＩ）、２，４’―ジフェニルメタンジイソシアネート（２，４’－ＭＤＩ）、１，４－フェニレンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）、テトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）、トリジンジイソシアネート（ＴＯＤＩ）、１，５－ナフタレンジイソシアネート（ＮＤＩ）などの芳香族イソシアネート；ヘキサメチレンイソシアネート（ＨＤＩ）、トリメチルヘキサメチレンジイソシアネート（ＴＭＨＤＩ）、リジンジイソシアネート、ノルボルナンジイソシアナートメチル（ＮＢＤＩ）などの脂肪族ポリイソシアネート；トランスシクロヘキサン－１，４－ジイソシアネート、イソホロンジイソシアネート（ＩＰＤＩ）、Ｈ６ＸＤＩ（水添ＸＤＩ）などの脂環式ポリイソシアネート等が挙げられる。これらの中でも、接着剤の無黄変性の観点から、ヘキサメチレンジイソシアネートが好ましい。
The diisocyanate is not particularly limited. For example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (4 , 4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI) ), Aromatic isocyanates such as 1,5-naphthalene diisocyanate (NDI); hexamethylene isocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate Aliphatic polyisocyanates such as Tomechiru (NBDI); trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), include alicyclic polyisocyanate such H6XDI (hydrogenated XDI). Among these, hexamethylene diisocyanate is preferred from the viewpoint of non-yellowing of the adhesive.
カルボン酸ジオールとしては、特に限定されず、例えば、ジメチロールブタン酸、ジメチロールプロピオン酸等が挙げられる。
The carboxylic acid diol is not particularly limited, and includes, for example, dimethylolbutanoic acid, dimethylolpropionic acid, and the like.
ポリエーテル骨格を有するウレタン（メタ）アクリレートとは、主鎖にポリエーテル構造とウレタン構造を有し、側鎖に（メタ）アクリル基を有するプレポリマーのことをいう。ポリエステル骨格を有するウレタン（メタ）アクリレートとは、主鎖にポリエステル構造とウレタン構造を有し、側鎖に（メタ）アクリル基を有するプレポリマーのことをいう。これらのプレポリマーは、ポリカーボネートジオールの代わりに、それぞれ、ポリエーテルジオール、ポリエステルジオールを用いること以外は上記ポリカーボネート骨格を有するウレタン（メタ）アクリレートと同様の方法により得ることができる。このとき、ポリエーテルジオール、ポリエステルジオールの好ましい重量平均分子量は、上述したポリカーボネートジオールの好ましい重量平均分子量と同じである。
ウ A urethane (meth) acrylate having a polyether skeleton refers to a prepolymer having a polyether structure and a urethane structure in a main chain, and having a (meth) acryl group in a side chain. The urethane (meth) acrylate having a polyester skeleton refers to a prepolymer having a polyester structure and a urethane structure in a main chain and having a (meth) acryl group in a side chain. These prepolymers can be obtained by the same method as for the urethane (meth) acrylate having a polycarbonate skeleton except that a polyether diol and a polyester diol are used instead of the polycarbonate diol, respectively. At this time, the preferable weight average molecular weight of the polyether diol and the polyester diol is the same as the preferable weight average molecular weight of the above-mentioned polycarbonate diol.
ＵＶ硬化型プレポリマーの重量平均分子量は、ＧＰＣによるポリスチレン換算で好ましくは１０，０００～１００，０００であり、より好ましくは３０，０００～７０，０００であり、さらに好ましくは４０，０００～６０，０００である。重量平均分子量が上記範囲であることにより、成膜性及び硬化性に一層優れる傾向にある。
The weight-average molecular weight of the UV-curable prepolymer is preferably from 10,000 to 100,000, more preferably from 30,000 to 70,000, even more preferably from 40,000 to 60,000 in terms of polystyrene by GPC. 000. When the weight average molecular weight is in the above range, the film formability and the curability tend to be more excellent.
ＵＶ硬化型プレポリマーの２重結合当量は、好ましくは１，０００～５，０００ｇ／ｅｑであり、より好ましくは１，５００～２，５００ｇ／ｅｑであり、さらに好ましくは１，８００～２，２００ｇ／ｅｑである。２重結合当量が上記範囲であることにより、硬化収縮の影響が少なくなったり、硬化が一層容易となる傾向にある。なお、２重結合当量は、カルボキシル基含有（メタ）アクリレートの固形分質量（ｇ）を、オキシラン環とエチレン性不飽和結合を有する化合物のモル数（ｇ/ｍｏｌ）で除すことにより算出した値をいう。
The double bond equivalent of the UV-curable prepolymer is preferably from 1,000 to 5,000 g / eq, more preferably from 1,500 to 2,500 g / eq, and still more preferably from 1,800 to 2,500 g / eq. It is 200 g / eq. When the double bond equivalent is in the above range, the influence of curing shrinkage is reduced, and curing tends to be easier. The double bond equivalent was calculated by dividing the solid content mass (g) of the carboxyl group-containing (meth) acrylate by the number of moles (g / mol) of the compound having an oxirane ring and an ethylenically unsaturated bond. Value.
色材の含有量は、ＵＶ硬化型プレポリマー１００質量部に対して、１～１０質量部程度であってもよい。なお、色材の含有量は、スラリー状態における質量部である。
The content of the coloring material may be about 1 to 10 parts by mass with respect to 100 parts by mass of the UV-curable prepolymer. The content of the coloring material is a part by mass in a slurry state.
〔ＵＶ硬化型モノマー〕
本実施形態の接着剤は、ＵＶ硬化型モノマーを含有してもよい。ＵＶ硬化型モノマーとしては、（メタ）アクリルモノマーが挙げられる。これらの（メタ）アクリルモノマーは、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、高温高湿環境下におけるヘイズの上昇を抑える観点から、水酸基含有（メタ）アクリルモノマーであることが好ましい。水酸基含有（メタ）アクリルモノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、５－ヒドロキシペンチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、カプロラクトン変性２－ヒドロキシエチル（メタ）アクリレート、ジエチレングリコール（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、２－アクリロイロキシエチル２－ヒドロキシエチルフタル酸、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－クロロ２－ヒドロキシプロピル（メタ）アクリレート、２，２－ジメチル２－ヒドロキシエチル（メタ）アクリレート等が挙げられる。 [UV curable monomer]
The adhesive of the present embodiment may contain a UV curable monomer. UV-curable monomers include (meth) acrylic monomers. These (meth) acrylic monomers are used alone or in combination of two or more. Among them, a hydroxyl group-containing (meth) acrylic monomer is preferable from the viewpoint of suppressing an increase in haze under a high temperature and high humidity environment. Examples of the hydroxyl group-containing (meth) acrylic monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyethyl (meth) acrylate. Hydroxyoctyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, 2-acryloyloxyethyl 2-hydroxyethyl phthalate, 2-hydroxypropyl (meth) ) Acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2,2-dimethyl2-hydroxyethyl (meth) acrylate And the like.
本実施形態の接着剤は、ＵＶ硬化型モノマーを含有してもよい。ＵＶ硬化型モノマーとしては、（メタ）アクリルモノマーが挙げられる。これらの（メタ）アクリルモノマーは、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、高温高湿環境下におけるヘイズの上昇を抑える観点から、水酸基含有（メタ）アクリルモノマーであることが好ましい。水酸基含有（メタ）アクリルモノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、５－ヒドロキシペンチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、カプロラクトン変性２－ヒドロキシエチル（メタ）アクリレート、ジエチレングリコール（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、２－アクリロイロキシエチル２－ヒドロキシエチルフタル酸、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－クロロ２－ヒドロキシプロピル（メタ）アクリレート、２，２－ジメチル２－ヒドロキシエチル（メタ）アクリレート等が挙げられる。 [UV curable monomer]
The adhesive of the present embodiment may contain a UV curable monomer. UV-curable monomers include (meth) acrylic monomers. These (meth) acrylic monomers are used alone or in combination of two or more. Among them, a hydroxyl group-containing (meth) acrylic monomer is preferable from the viewpoint of suppressing an increase in haze under a high temperature and high humidity environment. Examples of the hydroxyl group-containing (meth) acrylic monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyethyl (meth) acrylate. Hydroxyoctyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, 2-acryloyloxyethyl 2-hydroxyethyl phthalate, 2-hydroxypropyl (meth) ) Acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2,2-dimethyl2-hydroxyethyl (meth) acrylate And the like.
ＵＶ硬化型モノマーの含有量は、ＵＶ硬化型プレポリマー１００質量部に対して、２０～５０質量部程度であってもよい。
The content of the UV curable monomer may be about 20 to 50 parts by mass based on 100 parts by mass of the UV curable prepolymer.
〔光重合開始剤〕
本実施形態の接着剤は、光重合開始剤を含有してもよい。光重合開始剤としては、特に限定されず、例えば、アシルフォスフィンオキサイド系光重合開始剤、アルキルフェノン系光重合開始剤、分子内水素引き抜き型光重合開始剤等のいずれの光重合開始剤も用いられる。これらの中でも、反応性、硬化の均一性の観点から、光重合開始剤は、アシルフォスフィンオキサイド系光重合開始剤が好ましい。光重合開始剤の具体例としては、２，４，６－トリメチルベンゾイルフェニルホスフィンオキサイド、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、フェニルグリオキシリックアシッドメチルエステル等であり、これらの中でも、ラジカル発生効率が高く、深部硬化性の観点から、２，４，６－トリメチルベンゾイルフェニルホスフィンオキサイドが好ましい。
(Photopolymerization initiator)
The adhesive of the present embodiment may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited, for example, any photopolymerization initiator such as an acylphosphine oxide-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an intramolecular hydrogen abstraction type photopolymerization initiator. Used. Among these, from the viewpoint of reactivity and uniformity of curing, the photopolymerization initiator is preferably an acylphosphine oxide-based photopolymerization initiator. Specific examples of the photopolymerization initiator include 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethan-1-one, and phenylglyoxylic acid methyl ester. Among them, 2,4,6-trimethylbenzoylphenylphosphine oxide is preferred from the viewpoint of high radical generation efficiency and deep part curability.
本実施形態の接着剤は、光重合開始剤を含有してもよい。光重合開始剤としては、特に限定されず、例えば、アシルフォスフィンオキサイド系光重合開始剤、アルキルフェノン系光重合開始剤、分子内水素引き抜き型光重合開始剤等のいずれの光重合開始剤も用いられる。これらの中でも、反応性、硬化の均一性の観点から、光重合開始剤は、アシルフォスフィンオキサイド系光重合開始剤が好ましい。光重合開始剤の具体例としては、２，４，６－トリメチルベンゾイルフェニルホスフィンオキサイド、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、フェニルグリオキシリックアシッドメチルエステル等であり、これらの中でも、ラジカル発生効率が高く、深部硬化性の観点から、２，４，６－トリメチルベンゾイルフェニルホスフィンオキサイドが好ましい。
(Photopolymerization initiator)
The adhesive of the present embodiment may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited, for example, any photopolymerization initiator such as an acylphosphine oxide-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an intramolecular hydrogen abstraction type photopolymerization initiator. Used. Among these, from the viewpoint of reactivity and uniformity of curing, the photopolymerization initiator is preferably an acylphosphine oxide-based photopolymerization initiator. Specific examples of the photopolymerization initiator include 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethan-1-one, and phenylglyoxylic acid methyl ester. Among them, 2,4,6-trimethylbenzoylphenylphosphine oxide is preferred from the viewpoint of high radical generation efficiency and deep part curability.
光重合開始剤の含有量は、ＵＶ硬化型プレポリマー１００質量部に対して、０．５～５．０質量部程度であってもよい。
含有 The content of the photopolymerization initiator may be about 0.5 to 5.0 parts by mass based on 100 parts by mass of the UV-curable prepolymer.
〔シランカップリング剤〕
本実施形態の接着剤は、シランカップリング剤を含有してもよい。シランカップリング剤としては、例えば、モノマー型シランカップリング剤、アルコキシオリゴマー型シランカップリング剤、多官能型シランカップリング剤等のいずれのシランカップリング剤も用いることができる。これらの中でも、被着体がガラスである場合の接着性の観点から、シランカップリング剤は、（メタ）アクリル基を有するシランカップリング剤（（メタ）アクリル系シランカップリング剤）が好ましく、３－アクリロキシプロピルトリメトキシシランがより好ましい。 〔Silane coupling agent〕
The adhesive of the present embodiment may contain a silane coupling agent. As the silane coupling agent, for example, any silane coupling agent such as a monomer type silane coupling agent, an alkoxy oligomer type silane coupling agent, and a polyfunctional type silane coupling agent can be used. Among these, from the viewpoint of adhesion when the adherend is glass, the silane coupling agent is preferably a silane coupling agent having a (meth) acrylic group ((meth) acrylic silane coupling agent), 3-acryloxypropyltrimethoxysilane is more preferred.
本実施形態の接着剤は、シランカップリング剤を含有してもよい。シランカップリング剤としては、例えば、モノマー型シランカップリング剤、アルコキシオリゴマー型シランカップリング剤、多官能型シランカップリング剤等のいずれのシランカップリング剤も用いることができる。これらの中でも、被着体がガラスである場合の接着性の観点から、シランカップリング剤は、（メタ）アクリル基を有するシランカップリング剤（（メタ）アクリル系シランカップリング剤）が好ましく、３－アクリロキシプロピルトリメトキシシランがより好ましい。 〔Silane coupling agent〕
The adhesive of the present embodiment may contain a silane coupling agent. As the silane coupling agent, for example, any silane coupling agent such as a monomer type silane coupling agent, an alkoxy oligomer type silane coupling agent, and a polyfunctional type silane coupling agent can be used. Among these, from the viewpoint of adhesion when the adherend is glass, the silane coupling agent is preferably a silane coupling agent having a (meth) acrylic group ((meth) acrylic silane coupling agent), 3-acryloxypropyltrimethoxysilane is more preferred.
シランカップリング剤の含有量は、ＵＶ硬化型プレポリマー１００質量部に対して、０．１～１０質量部程度であってもよい。
含有 The content of the silane coupling agent may be about 0.1 to 10 parts by mass with respect to 100 parts by mass of the UV-curable prepolymer.
〔その他の成分〕
本実施形態の接着剤は、シリカ、アルミナ、水和アルミナ等の各種フィラー、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、レベリング剤、消泡剤、着色顔料、有機溶媒等の、通常接着剤に添加されることがある添加剤を含んでもよい。 [Other components]
The adhesive of the present embodiment includes various fillers such as silica, alumina, and hydrated alumina, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, leveling agents, defoamers, coloring pigments, organic solvents, and the like. , And may include additives that are usually added to the adhesive.
本実施形態の接着剤は、シリカ、アルミナ、水和アルミナ等の各種フィラー、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、レベリング剤、消泡剤、着色顔料、有機溶媒等の、通常接着剤に添加されることがある添加剤を含んでもよい。 [Other components]
The adhesive of the present embodiment includes various fillers such as silica, alumina, and hydrated alumina, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, leveling agents, defoamers, coloring pigments, organic solvents, and the like. , And may include additives that are usually added to the adhesive.
本実施形態の接着剤では、光硬化後において、ヘイズが５．０％以下であることが好ましく、４．０％以下であることがより好ましく、３．０％以下であることが更に好ましい。ヘイズが上記範囲内であることにより、接着剤は、透明性に一層優れる傾向にある。なお、ヘイズは、後述する実施例に記載の方法により求められる。
で は In the adhesive of the present embodiment, the haze after photocuring is preferably 5.0% or less, more preferably 4.0% or less, and even more preferably 3.0% or less. When the haze is within the above range, the adhesive tends to be more excellent in transparency. In addition, haze is determined by a method described in Examples described later.
本実施形態の接着剤では、光硬化後において、透過率が４０～６０％であることが好ましく、４５～５５％であることがより好ましい。透過率が上記範囲内であることにより、接着剤は、ニュートラルグレイを維持しつつ、視認性に一層優れる傾向にある。透過率は、後述する実施例に記載の方法により求められる。
接着 In the adhesive of the present embodiment, the transmittance after photocuring is preferably 40 to 60%, more preferably 45 to 55%. When the transmittance is within the above range, the adhesive tends to be more excellent in visibility while maintaining neutral gray. The transmittance is determined by the method described in Examples described later.
本実施形態の接着剤では、光硬化後において、色相変化△Ｅが１．０以下であることが好ましく、０．８以下であることがより好ましく、０．５以下であることが更に好ましい。△Ｅが上記範囲内であることにより、接着剤は、耐環境性に一層優れる傾向にある。△Ｅは、後述する実施例に記載の方法により求められる。
In the adhesive of the present embodiment, the hue change ΔE after photo-curing is preferably 1.0 or less, more preferably 0.8 or less, and even more preferably 0.5 or less. When ΔE is within the above range, the adhesive tends to be more excellent in environmental resistance. ΔE is determined by a method described in Examples described later.
本実施形態の接着剤は、ディスプレイ貼付用に用いられる。ディスプレイとしては、例えば、液晶ディスプレイ、プラズマディスプレイ、ＣＲＴ、エレクトロルミネッセンス、タッチスクリーンパネル等の電子ディスプレイが挙げられる。これらの中でも、タッチセンサの機能を損なう虞れが少ないため、タッチスクリーンパネルが好ましい。また、本実施形態の接着剤は外光反射を有効に抑制できるため、電子ディスプレイは、車載用であることが好ましい。
接着 The adhesive of this embodiment is used for attaching a display. Examples of the display include an electronic display such as a liquid crystal display, a plasma display, a CRT, electroluminescence, and a touch screen panel. Among them, the touch screen panel is preferable because the function of the touch sensor is less likely to be impaired. Further, since the adhesive of the present embodiment can effectively suppress the reflection of external light, the electronic display is preferably for a vehicle.
〔接着シート〕
本実施形態の接着シートは、本実施形態の接着剤を含む。接着シートは、例えば、第１の基材と、接着層と、第２の基材とがこの順序で積層されており、接着層が本実施形態の接着剤で構成されている。第１の基材及び第２の基材は、例えば、剥離性を有する公知の基材（例えば、ＰＥＴフィルム等）であってもよい。接着シートの厚さは、例えば、１０～２５０μｍ程度であってもよい。 [Adhesive sheet]
The adhesive sheet of the present embodiment includes the adhesive of the present embodiment. In the adhesive sheet, for example, a first base material, an adhesive layer, and a second base material are laminated in this order, and the adhesive layer is formed of the adhesive of the present embodiment. The first base material and the second base material may be, for example, a known base material having releasability (for example, a PET film or the like). The thickness of the adhesive sheet may be, for example, about 10 to 250 μm.
本実施形態の接着シートは、本実施形態の接着剤を含む。接着シートは、例えば、第１の基材と、接着層と、第２の基材とがこの順序で積層されており、接着層が本実施形態の接着剤で構成されている。第１の基材及び第２の基材は、例えば、剥離性を有する公知の基材（例えば、ＰＥＴフィルム等）であってもよい。接着シートの厚さは、例えば、１０～２５０μｍ程度であってもよい。 [Adhesive sheet]
The adhesive sheet of the present embodiment includes the adhesive of the present embodiment. In the adhesive sheet, for example, a first base material, an adhesive layer, and a second base material are laminated in this order, and the adhesive layer is formed of the adhesive of the present embodiment. The first base material and the second base material may be, for example, a known base material having releasability (for example, a PET film or the like). The thickness of the adhesive sheet may be, for example, about 10 to 250 μm.
なお、本明細書中の各物性は、特に明記しない限り、以下の実施例に記載された方法に準じて測定することができる。
各 Unless otherwise specified, each property in this specification can be measured according to the methods described in the following examples.
以下、本発明を実施例及び比較例によってさらに具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples.
［合成例１］〔ＵＶ硬化型プレポリマー（Ａ）の合成〕
温度計、冷却管、撹拌装置を備えた４つ口フラスコに、ヘキサメチレンジイソシアネート（東ソー株式会社製、品名：ＨＤＩ、略名ＨＤＩ）３３．３質量部と、重量平均分子量４００のポリカーボネートジオール５９．４質量部と、ジメチロールブタン酸７．３質量部と、触媒としてジブチル錫ラウレート等の有機錫化合物１質量部と、有機溶媒としてメチルエチルケトン１００質量部を反応容器に入れ、７０℃で２４時間反応させた。
得られた合成物の反応状況を確認するため、ＩＲ測定機器を用いて分析を行った。ＩＲチャートにおいて当該合成物のＮＣＯ特性吸収（２２７０ｃｍ－１）が消失していることを確認し、合成物がカルボキシル基を有するウレタンアクリレートであることを確認した。
次に、得られたカルボキシル基を有するウレタンアクリレート１００質量部と、グリシジルメタクリレート７．１質量部と、触媒としてトリエチルアミン０．７質量部と、重合禁止剤としてハイドロキノン０．０５質量部とを反応容器に入れ、７５℃で１２時間反応を行い、付加反応させることによりウレタン（メタ）アクリレート系ポリマーであるＵＶ硬化型プレポリマー（Ａ）を得た。
なお、付加反応は、以下の方法に従って測定した酸価が１．０ｍｇＫＯＨ／ｇ以下になった時点で終了させた。また、得られたＵＶ硬化型プレポリマー（Ａ）は、重量平均分子量５０，０００、固形分濃度５０質量％、２重結合当量２，０００ｇ／ｅｑ、Ｔｇ５℃であった。
Ｔｇは、動的粘弾性測定（ＤＭＡ：Ｄｙｎａｍｉｃ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｓｉｓ）を用いて、ＴＡＮδ（引張損失弾性率Ｅ″/引張貯蔵弾性率Ｅ′）のピーク値から求めることができる。動的粘弾性は、例えば、幅５ｍｍ、長さ５０ｍｍ、厚み０．１μｍの試験片を用いて測定することができる。
２重結合当量は、二重結合１ｍｏｌあたりの重合体の質量で表され、以下の式で算出される。
２重結合当量（ｇ／ｅｑ）＝（メタ）アクリル系重合体の質量（ｇ）／（メタ）アクリル系重合体の二重結合含有モル量（ｍｏｌ） [Synthesis Example 1] [Synthesis of UV-curable prepolymer (A)]
In a four-necked flask equipped with a thermometer, a condenser, and a stirrer, 33.3 parts by mass of hexamethylene diisocyanate (manufactured by Tosoh Corp., product name: HDI, abbreviated name HDI) and polycarbonate diol having a weight average molecular weight of 400 were placed. 4 parts by mass, 7.3 parts by mass of dimethylolbutanoic acid, 1 part by mass of an organotin compound such as dibutyltin laurate as a catalyst, and 100 parts by mass of methyl ethyl ketone as an organic solvent are placed in a reaction vessel and reacted at 70 ° C. for 24 hours. I let it.
In order to confirm the reaction status of the obtained synthesized product, analysis was performed using an IR measuring instrument. In the IR chart, it was confirmed that the NCO characteristic absorption (2270 cm -1 ) of the compound disappeared, and it was confirmed that the compound was urethane acrylate having a carboxyl group.
Next, 100 parts by mass of the obtained urethane acrylate having a carboxyl group, 7.1 parts by mass of glycidyl methacrylate, 0.7 parts by mass of triethylamine as a catalyst, and 0.05 parts by mass of hydroquinone as a polymerization inhibitor were placed in a reaction vessel. And a reaction was performed at 75 ° C. for 12 hours, and an addition reaction was performed to obtain a UV-curable prepolymer (A), which is a urethane (meth) acrylate polymer.
The addition reaction was terminated when the acid value measured according to the following method became 1.0 mgKOH / g or less. In addition, the obtained UV-curable prepolymer (A) had a weight average molecular weight of 50,000, a solid content concentration of 50% by mass, a double bond equivalent of 2,000 g / eq, and a Tg of 5 ° C.
Tg can be determined from the peak value of TANδ (tensile loss modulus E ″ / tensile storage modulus E ′) using dynamic viscoelasticity measurement (DMA: Dynamic Mechanical Analysis). For example, it can be measured using a test piece having a width of 5 mm, a length of 50 mm, and a thickness of 0.1 μm.
The double bond equivalent is represented by the mass of the polymer per 1 mol of the double bond, and is calculated by the following formula.
Double bond equivalent (g / eq) = mass (g) of (meth) acrylic polymer / molar amount of double bond (mol) of (meth) acrylic polymer
温度計、冷却管、撹拌装置を備えた４つ口フラスコに、ヘキサメチレンジイソシアネート（東ソー株式会社製、品名：ＨＤＩ、略名ＨＤＩ）３３．３質量部と、重量平均分子量４００のポリカーボネートジオール５９．４質量部と、ジメチロールブタン酸７．３質量部と、触媒としてジブチル錫ラウレート等の有機錫化合物１質量部と、有機溶媒としてメチルエチルケトン１００質量部を反応容器に入れ、７０℃で２４時間反応させた。
得られた合成物の反応状況を確認するため、ＩＲ測定機器を用いて分析を行った。ＩＲチャートにおいて当該合成物のＮＣＯ特性吸収（２２７０ｃｍ－１）が消失していることを確認し、合成物がカルボキシル基を有するウレタンアクリレートであることを確認した。
次に、得られたカルボキシル基を有するウレタンアクリレート１００質量部と、グリシジルメタクリレート７．１質量部と、触媒としてトリエチルアミン０．７質量部と、重合禁止剤としてハイドロキノン０．０５質量部とを反応容器に入れ、７５℃で１２時間反応を行い、付加反応させることによりウレタン（メタ）アクリレート系ポリマーであるＵＶ硬化型プレポリマー（Ａ）を得た。
なお、付加反応は、以下の方法に従って測定した酸価が１．０ｍｇＫＯＨ／ｇ以下になった時点で終了させた。また、得られたＵＶ硬化型プレポリマー（Ａ）は、重量平均分子量５０，０００、固形分濃度５０質量％、２重結合当量２，０００ｇ／ｅｑ、Ｔｇ５℃であった。
Ｔｇは、動的粘弾性測定（ＤＭＡ：Ｄｙｎａｍｉｃ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｓｉｓ）を用いて、ＴＡＮδ（引張損失弾性率Ｅ″/引張貯蔵弾性率Ｅ′）のピーク値から求めることができる。動的粘弾性は、例えば、幅５ｍｍ、長さ５０ｍｍ、厚み０．１μｍの試験片を用いて測定することができる。
２重結合当量は、二重結合１ｍｏｌあたりの重合体の質量で表され、以下の式で算出される。
２重結合当量（ｇ／ｅｑ）＝（メタ）アクリル系重合体の質量（ｇ）／（メタ）アクリル系重合体の二重結合含有モル量（ｍｏｌ） [Synthesis Example 1] [Synthesis of UV-curable prepolymer (A)]
In a four-necked flask equipped with a thermometer, a condenser, and a stirrer, 33.3 parts by mass of hexamethylene diisocyanate (manufactured by Tosoh Corp., product name: HDI, abbreviated name HDI) and polycarbonate diol having a weight average molecular weight of 400 were placed. 4 parts by mass, 7.3 parts by mass of dimethylolbutanoic acid, 1 part by mass of an organotin compound such as dibutyltin laurate as a catalyst, and 100 parts by mass of methyl ethyl ketone as an organic solvent are placed in a reaction vessel and reacted at 70 ° C. for 24 hours. I let it.
In order to confirm the reaction status of the obtained synthesized product, analysis was performed using an IR measuring instrument. In the IR chart, it was confirmed that the NCO characteristic absorption (2270 cm -1 ) of the compound disappeared, and it was confirmed that the compound was urethane acrylate having a carboxyl group.
Next, 100 parts by mass of the obtained urethane acrylate having a carboxyl group, 7.1 parts by mass of glycidyl methacrylate, 0.7 parts by mass of triethylamine as a catalyst, and 0.05 parts by mass of hydroquinone as a polymerization inhibitor were placed in a reaction vessel. And a reaction was performed at 75 ° C. for 12 hours, and an addition reaction was performed to obtain a UV-curable prepolymer (A), which is a urethane (meth) acrylate polymer.
The addition reaction was terminated when the acid value measured according to the following method became 1.0 mgKOH / g or less. In addition, the obtained UV-curable prepolymer (A) had a weight average molecular weight of 50,000, a solid content concentration of 50% by mass, a double bond equivalent of 2,000 g / eq, and a Tg of 5 ° C.
Tg can be determined from the peak value of TANδ (tensile loss modulus E ″ / tensile storage modulus E ′) using dynamic viscoelasticity measurement (DMA: Dynamic Mechanical Analysis). For example, it can be measured using a test piece having a width of 5 mm, a length of 50 mm, and a thickness of 0.1 μm.
The double bond equivalent is represented by the mass of the polymer per 1 mol of the double bond, and is calculated by the following formula.
Double bond equivalent (g / eq) = mass (g) of (meth) acrylic polymer / molar amount of double bond (mol) of (meth) acrylic polymer
（酸価測定方法）
ここで、酸価はＪＩＳ Ｋ ５６０１に準拠して測定した。
樹脂の固形分１ｇを秤量し、混合溶剤（質量比：トルエン／メタノール＝５０／５０）を加えて溶解後、指示薬としてフェノールフタレイン溶液を適量添加し、０．ｌＮの水酸化カリウム水溶液で滴定し、下記式（α）により酸価を測定した。
ｘ＝１０×Ｖｆ×５６．１／（Ｗｐ×Ｉ）・・・（α）
（式（α）中、ｘは酸価（ｍｇＫＯＨ／ｇ）を示し、Ｖｆは０．１ＮのＫＯＨ水溶液の滴定量（ｍＬ）を示し、Ｗｐは測定した樹脂溶液の質量（ｇ）を示し、Ｉは測定した樹脂溶液中の不揮発分の割合を（質量％）を示す。） (Method of measuring acid value)
Here, the acid value was measured according to JIS K5601.
After weighing 1 g of the solid content of the resin and adding and dissolving a mixed solvent (mass ratio: toluene / methanol = 50/50), an appropriate amount of a phenolphthalein solution was added as an indicator. Titration was performed with an 1N aqueous solution of potassium hydroxide, and the acid value was measured by the following formula (α).
x = 10 × Vf × 56.1 / (Wp × I) (α)
(In the formula (α), x represents an acid value (mg KOH / g), Vf represents a titer (mL) of a 0.1 N KOH aqueous solution, Wp represents a measured mass (g) of the resin solution, I indicates the measured ratio of nonvolatile components in the resin solution (% by mass).)
ここで、酸価はＪＩＳ Ｋ ５６０１に準拠して測定した。
樹脂の固形分１ｇを秤量し、混合溶剤（質量比：トルエン／メタノール＝５０／５０）を加えて溶解後、指示薬としてフェノールフタレイン溶液を適量添加し、０．ｌＮの水酸化カリウム水溶液で滴定し、下記式（α）により酸価を測定した。
ｘ＝１０×Ｖｆ×５６．１／（Ｗｐ×Ｉ）・・・（α）
（式（α）中、ｘは酸価（ｍｇＫＯＨ／ｇ）を示し、Ｖｆは０．１ＮのＫＯＨ水溶液の滴定量（ｍＬ）を示し、Ｗｐは測定した樹脂溶液の質量（ｇ）を示し、Ｉは測定した樹脂溶液中の不揮発分の割合を（質量％）を示す。） (Method of measuring acid value)
Here, the acid value was measured according to JIS K5601.
After weighing 1 g of the solid content of the resin and adding and dissolving a mixed solvent (mass ratio: toluene / methanol = 50/50), an appropriate amount of a phenolphthalein solution was added as an indicator. Titration was performed with an 1N aqueous solution of potassium hydroxide, and the acid value was measured by the following formula (α).
x = 10 × Vf × 56.1 / (Wp × I) (α)
(In the formula (α), x represents an acid value (mg KOH / g), Vf represents a titer (mL) of a 0.1 N KOH aqueous solution, Wp represents a measured mass (g) of the resin solution, I indicates the measured ratio of nonvolatile components in the resin solution (% by mass).)
（重量平均分子量測定方法）
ここで、重量平均分子量は、平均分子量が約５００～約１００万の標準ポリスチレンを用いてＧＰＣにより測定した。
装置：東ソー製ＨＬＣ－８１２０ＧＰＣ
カラムＴＳＫｇｅｌ ＳｕｐｅｒＭ Ｍを１本とＴＳＫｇｅｌ ＳｕｐｅｒＨ－２０００を２本の計３本を直列接続
カラム温度： ４０℃
移動相： ＴＨＦ （ＢＨＴ有）
流量： ０．３ｍ１／ｍｉｎ
検出器：示差屈折率検出器
測定温度： ４０℃ (Weight average molecular weight measurement method)
Here, the weight average molecular weight was measured by GPC using standard polystyrene having an average molecular weight of about 500 to about 1,000,000.
Equipment: Tosoh HLC-8120GPC
One column TSKgel SuperM M and two TSKgel SuperH-2000 are connected in series. A total of three columns Column temperature: 40 ° C
Mobile phase: THF (with BHT)
Flow rate: 0.3m1 / min
Detector: Differential refractive index detector Measurement temperature: 40 ° C
ここで、重量平均分子量は、平均分子量が約５００～約１００万の標準ポリスチレンを用いてＧＰＣにより測定した。
装置：東ソー製ＨＬＣ－８１２０ＧＰＣ
カラムＴＳＫｇｅｌ ＳｕｐｅｒＭ Ｍを１本とＴＳＫｇｅｌ ＳｕｐｅｒＨ－２０００を２本の計３本を直列接続
カラム温度： ４０℃
移動相： ＴＨＦ （ＢＨＴ有）
流量： ０．３ｍ１／ｍｉｎ
検出器：示差屈折率検出器
測定温度： ４０℃ (Weight average molecular weight measurement method)
Here, the weight average molecular weight was measured by GPC using standard polystyrene having an average molecular weight of about 500 to about 1,000,000.
Equipment: Tosoh HLC-8120GPC
One column TSKgel SuperM M and two TSKgel SuperH-2000 are connected in series. A total of three columns Column temperature: 40 ° C
Mobile phase: THF (with BHT)
Flow rate: 0.3m1 / min
Detector: Differential refractive index detector Measurement temperature: 40 ° C
［合成例２］〔ＵＶ硬化型プレポリマー（Ｂ）の合成〕
ポリカーボネートジオールに代えてポリエーテルジオールを用いたこと以外は合成例１と同様の方法により、ＵＶ硬化型プレポリマー（Ｂ）を得た。 [Synthesis Example 2] [Synthesis of UV-curable prepolymer (B)]
A UV-curable prepolymer (B) was obtained in the same manner as in Synthesis Example 1 except that polyether diol was used instead of polycarbonate diol.
ポリカーボネートジオールに代えてポリエーテルジオールを用いたこと以外は合成例１と同様の方法により、ＵＶ硬化型プレポリマー（Ｂ）を得た。 [Synthesis Example 2] [Synthesis of UV-curable prepolymer (B)]
A UV-curable prepolymer (B) was obtained in the same manner as in Synthesis Example 1 except that polyether diol was used instead of polycarbonate diol.
［合成例３］〔ＵＶ硬化型プレポリマー（Ｃ）の合成〕
ポリカーボネートジオールに代えてポリエステルジオールを用いたこと以外は合成例１と同様の方法により、ＵＶ硬化型プレポリマー（Ｃ）を得た。 [Synthesis Example 3] [Synthesis of UV-curable prepolymer (C)]
A UV-curable prepolymer (C) was obtained in the same manner as in Synthesis Example 1 except that polyester diol was used instead of polycarbonate diol.
ポリカーボネートジオールに代えてポリエステルジオールを用いたこと以外は合成例１と同様の方法により、ＵＶ硬化型プレポリマー（Ｃ）を得た。 [Synthesis Example 3] [Synthesis of UV-curable prepolymer (C)]
A UV-curable prepolymer (C) was obtained in the same manner as in Synthesis Example 1 except that polyester diol was used instead of polycarbonate diol.
〔実施例１～１６及び比較例１～４〕
表１～表４に示す各成分を、表１～表４に示す添加量で添加して撹拌し、接着剤（樹脂組成物）を得た。また、添加の際に溶剤としてメチルエチルケトンを１００質量部程度加えながら粘度を調整した。なお、表１中の数字は固形分量を示す。また、表中に記載中、「４－ＨＢＡ」は、４－ヒドロキシブチルアクリレートを示し、「ＴＰＯ」は、２，４，６－トリメチルベンゾイルフェニルホスフィンオキサイドを示す。 [Examples 1 to 16 and Comparative Examples 1 to 4]
The components shown in Tables 1 to 4 were added in the amounts shown in Tables 1 to 4 and stirred to obtain an adhesive (resin composition). The viscosity was adjusted while adding about 100 parts by mass of methyl ethyl ketone as a solvent during the addition. In addition, the number in Table 1 shows solid content. In the table, "4-HBA" indicates 4-hydroxybutyl acrylate, and "TPO" indicates 2,4,6-trimethylbenzoylphenylphosphine oxide.
表１～表４に示す各成分を、表１～表４に示す添加量で添加して撹拌し、接着剤（樹脂組成物）を得た。また、添加の際に溶剤としてメチルエチルケトンを１００質量部程度加えながら粘度を調整した。なお、表１中の数字は固形分量を示す。また、表中に記載中、「４－ＨＢＡ」は、４－ヒドロキシブチルアクリレートを示し、「ＴＰＯ」は、２，４，６－トリメチルベンゾイルフェニルホスフィンオキサイドを示す。 [Examples 1 to 16 and Comparative Examples 1 to 4]
The components shown in Tables 1 to 4 were added in the amounts shown in Tables 1 to 4 and stirred to obtain an adhesive (resin composition). The viscosity was adjusted while adding about 100 parts by mass of methyl ethyl ketone as a solvent during the addition. In addition, the number in Table 1 shows solid content. In the table, "4-HBA" indicates 4-hydroxybutyl acrylate, and "TPO" indicates 2,4,6-trimethylbenzoylphenylphosphine oxide.
得られた接着剤を乾燥後の厚さが２５μｍとなるように離型ＰＥＴ５０μｍ上に塗布し、１３０℃で５分間乾燥させた後、反対面に離型ＰＥＴ３８μｍを設置し、接着シートを得た。得られた接着シートを用いて、各物性の評価を行った。
また、接着剤の厚さは、ミツトヨ製ＶＡ－５０Ａを使用して、接着シート全体の厚さを測定し、そこから離型ＰＥＴの厚みを差し引くことにより求めた。 The obtained adhesive was applied on release PET 50 μm so that the thickness after drying was 25 μm, and dried at 130 ° C. for 5 minutes. Then, release PET 38 μm was placed on the opposite surface to obtain an adhesive sheet. . Each physical property was evaluated using the obtained adhesive sheet.
The thickness of the adhesive was determined by measuring the thickness of the entire adhesive sheet using VA-50A manufactured by Mitutoyo, and subtracting the thickness of the release PET therefrom.
また、接着剤の厚さは、ミツトヨ製ＶＡ－５０Ａを使用して、接着シート全体の厚さを測定し、そこから離型ＰＥＴの厚みを差し引くことにより求めた。 The obtained adhesive was applied on release PET 50 μm so that the thickness after drying was 25 μm, and dried at 130 ° C. for 5 minutes. Then, release PET 38 μm was placed on the opposite surface to obtain an adhesive sheet. . Each physical property was evaluated using the obtained adhesive sheet.
The thickness of the adhesive was determined by measuring the thickness of the entire adhesive sheet using VA-50A manufactured by Mitutoyo, and subtracting the thickness of the release PET therefrom.
〔色相評価〕
得られた接着シートの片側離型ＰＥＴを剥離し、富士フィルム製「ＴＡＣフィルム」８０μｍ厚さ（４０ｍｍ角）へロールラミネートにより貼り合わせた。ロールラミネートは、温度２５～５０℃、圧力０．１～０．４ＭＰａ、速度０．５～１．０ｍ／ｍｉｎで実施した。接着シートのもう片側の離型ＰＥＴフィルムを剥離した側に三菱ガス化学製ポリカーボネートフィルム厚さ１．０ｍｍ（４０ｍｍ角）を真空ラミネートにより貼り合せた。真空ラミネートは、温度２５～５０℃、圧力０．１～０．５ＭＰａ、真空引き１０ｓ、加圧１０ｓで実施した。その後オートクレーブ処理を行った。オートクレーブは温度６０℃、圧力０．６ＭＰａ、時間１ｈｒにて実施した。ＵＶ露光は超高圧水銀ランプ光源を用いて、λ＝３６５ｎｍにおける積算光量が３０００ｍＪ／ｃｍ２となるように実施した。このようにして評価用サンプルを得た。 (Hue evaluation)
The one-sided release PET of the obtained adhesive sheet was peeled off, and bonded to a “TAC film” made by Fuji Film with a thickness of 80 μm (40 mm square) by roll lamination. Roll lamination was performed at a temperature of 25 to 50 ° C., a pressure of 0.1 to 0.4 MPa, and a speed of 0.5 to 1.0 m / min. On the other side of the adhesive sheet from which the release PET film was peeled off, a polycarbonate film having a thickness of 1.0 mm (40 mm square) manufactured by Mitsubishi Gas Chemical was bonded by vacuum lamination. Vacuum lamination was performed at a temperature of 25 to 50 ° C., a pressure of 0.1 to 0.5 MPa, a vacuum evacuation of 10 s, and a pressure of 10 s. Thereafter, an autoclave treatment was performed. The autoclave was performed at a temperature of 60 ° C., a pressure of 0.6 MPa, and a time of 1 hour. UV exposure was performed using an ultra-high pressure mercury lamp light source such that the integrated light amount at λ = 365 nm was 3000 mJ / cm 2 . Thus, an evaluation sample was obtained.
得られた接着シートの片側離型ＰＥＴを剥離し、富士フィルム製「ＴＡＣフィルム」８０μｍ厚さ（４０ｍｍ角）へロールラミネートにより貼り合わせた。ロールラミネートは、温度２５～５０℃、圧力０．１～０．４ＭＰａ、速度０．５～１．０ｍ／ｍｉｎで実施した。接着シートのもう片側の離型ＰＥＴフィルムを剥離した側に三菱ガス化学製ポリカーボネートフィルム厚さ１．０ｍｍ（４０ｍｍ角）を真空ラミネートにより貼り合せた。真空ラミネートは、温度２５～５０℃、圧力０．１～０．５ＭＰａ、真空引き１０ｓ、加圧１０ｓで実施した。その後オートクレーブ処理を行った。オートクレーブは温度６０℃、圧力０．６ＭＰａ、時間１ｈｒにて実施した。ＵＶ露光は超高圧水銀ランプ光源を用いて、λ＝３６５ｎｍにおける積算光量が３０００ｍＪ／ｃｍ２となるように実施した。このようにして評価用サンプルを得た。 (Hue evaluation)
The one-sided release PET of the obtained adhesive sheet was peeled off, and bonded to a “TAC film” made by Fuji Film with a thickness of 80 μm (40 mm square) by roll lamination. Roll lamination was performed at a temperature of 25 to 50 ° C., a pressure of 0.1 to 0.4 MPa, and a speed of 0.5 to 1.0 m / min. On the other side of the adhesive sheet from which the release PET film was peeled off, a polycarbonate film having a thickness of 1.0 mm (40 mm square) manufactured by Mitsubishi Gas Chemical was bonded by vacuum lamination. Vacuum lamination was performed at a temperature of 25 to 50 ° C., a pressure of 0.1 to 0.5 MPa, a vacuum evacuation of 10 s, and a pressure of 10 s. Thereafter, an autoclave treatment was performed. The autoclave was performed at a temperature of 60 ° C., a pressure of 0.6 MPa, and a time of 1 hour. UV exposure was performed using an ultra-high pressure mercury lamp light source such that the integrated light amount at λ = 365 nm was 3000 mJ / cm 2 . Thus, an evaluation sample was obtained.
ＪＩＳ Ｚ８７２２に準じ、分光光度計（日立ハイテクノロジー製 Ｕ－４１００）を用いて測定した。測定条件はＣ光源、透過にて実施し、波長λ＝３８０～７６０ｎｍにおけるＬ＊、ａ＊、ｂ＊を測定した。
◎：ａ＊≦±１．０、ｂ＊≦±１．０
○：±１．０＜ａ＊≦±３．０、±１．０＜ｂ＊≦±３．０
×：±３．０＜ａ＊、±３．０＜ｂ＊ The measurement was performed using a spectrophotometer (U-4100, manufactured by Hitachi High-Technology) according to JIS Z8722. The measurement was performed using a C light source and transmission, and L * , a * , and b * at wavelengths λ = 380 to 760 nm were measured.
：: a * ≦ ± 1.0, b * ≦ ± 1.0
：: ± 1.0 <a * ≦ ± 3.0, ± 1.0 <b * ≦ ± 3.0
×: ± 3.0 <a * , ± 3.0 <b *
◎：ａ＊≦±１．０、ｂ＊≦±１．０
○：±１．０＜ａ＊≦±３．０、±１．０＜ｂ＊≦±３．０
×：±３．０＜ａ＊、±３．０＜ｂ＊ The measurement was performed using a spectrophotometer (U-4100, manufactured by Hitachi High-Technology) according to JIS Z8722. The measurement was performed using a C light source and transmission, and L * , a * , and b * at wavelengths λ = 380 to 760 nm were measured.
：: a * ≦ ± 1.0, b * ≦ ± 1.0
：: ± 1.0 <a * ≦ ± 3.0, ± 1.0 <b * ≦ ± 3.0
×: ± 3.0 <a * , ± 3.0 <b *
〔透過率評価〕
〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。ＪＩＳ Ｋ７１３６に準じて測定した。
〇：透過率が５０±５％以内であった。
×：透過率が４５％未満又は５５％を超えていた。 (Transmissivity evaluation)
The same evaluation sample as that prepared in the section [Hue evaluation] was used. It was measured according to JIS K7136.
〇: The transmittance was within 50 ± 5%.
X: The transmittance was less than 45% or more than 55%.
〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。ＪＩＳ Ｋ７１３６に準じて測定した。
〇：透過率が５０±５％以内であった。
×：透過率が４５％未満又は５５％を超えていた。 (Transmissivity evaluation)
The same evaluation sample as that prepared in the section [Hue evaluation] was used. It was measured according to JIS K7136.
〇: The transmittance was within 50 ± 5%.
X: The transmittance was less than 45% or more than 55%.
〔ヘイズ評価〕
〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。ＪＩＳ Ｋ７１３６に準じ、ヘイズメーター（村上色彩技術研究所ＨＭ－１５０）を用いて測定した。
◎・・・ヘイズ≦２．０％
○・・・２．０％＜ヘイズ≦５．０％
×・・・５．０％＜ヘイズ [Haze evaluation]
The same evaluation sample as that prepared in the section [Hue evaluation] was used. According to JIS K7136, it was measured using a haze meter (Murakami Color Research Laboratory HM-150).
◎ ・ ・ ・ Haze ≦ 2.0%
○ ・ ・ ・ 2.0% <Haze ≦ 5.0%
×: 5.0% <Haze
〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。ＪＩＳ Ｋ７１３６に準じ、ヘイズメーター（村上色彩技術研究所ＨＭ－１５０）を用いて測定した。
◎・・・ヘイズ≦２．０％
○・・・２．０％＜ヘイズ≦５．０％
×・・・５．０％＜ヘイズ [Haze evaluation]
The same evaluation sample as that prepared in the section [Hue evaluation] was used. According to JIS K7136, it was measured using a haze meter (Murakami Color Research Laboratory HM-150).
◎ ・ ・ ・ Haze ≦ 2.0%
○ ・ ・ ・ 2.0% <Haze ≦ 5.0%
×: 5.0% <Haze
〔耐候性〕
〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。初期値（Ｌ＊、ａ＊、ｂ＊）を色相測定方法と同様に測定した。その後、ＪＩＳ Ｄ ０２０５に準じた耐候性評価に３００ｈ投入した後のＬ＊、ａ＊、ｂ＊を測定し、次式により△Ｅを算出した。
尚、耐候性評価はスガ試験機株式会社製、低温キセノンウェザーメーターＸＬ－７５を使用した。条件はブラックパネル温度６３±３℃、水の噴射条件（圧力０．０８～０．１３ＭＰａ、水量６６０±６０ｍｌ／分、噴射時間１２分／６０分照射、水温１６±５℃）、相対湿度５０±５％、試料面放射照度６０±３Ｗ／ｍ２（３００～４００ｎｍ）、１８０±３Ｗ／ｍ２（３００～４００ｎｍ）。
△Ｅ＝［（△Ｌ＊）２＋（△ａ＊）２＋（△ｂ＊）２］１／２
○・・・△Ｅ≦１．０
×・・・１．０＜△Ｅ 〔Weatherability〕
The same evaluation sample as that prepared in the section [Hue evaluation] was used. Initial values (L * , a * , b * ) were measured in the same manner as in the hue measurement method. Thereafter, L * , a * , and b * were measured after 300 hours in the weather resistance evaluation according to JIS D 0205, and ΔE was calculated by the following equation.
The weather resistance was evaluated using a low temperature xenon weather meter XL-75 manufactured by Suga Test Instruments Co., Ltd. The conditions are black panel temperature 63 ± 3 ° C, water injection conditions (pressure 0.08 to 0.13MPa, water amount 660 ± 60ml / min, injection time 12 minutes / 60 minutes, water temperature 16 ± 5 ° C), relative humidity 50 ± 5%, sample surface irradiance 60 ± 3 W / m 2 (300 to 400 nm), 180 ± 3 W / m 2 (300 to 400 nm).
ΔE = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ] 1/2
○ ・ ・ ・ △ E ≦ 1.0
× ・ ・ ・ 1.0 <△ E
〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。初期値（Ｌ＊、ａ＊、ｂ＊）を色相測定方法と同様に測定した。その後、ＪＩＳ Ｄ ０２０５に準じた耐候性評価に３００ｈ投入した後のＬ＊、ａ＊、ｂ＊を測定し、次式により△Ｅを算出した。
尚、耐候性評価はスガ試験機株式会社製、低温キセノンウェザーメーターＸＬ－７５を使用した。条件はブラックパネル温度６３±３℃、水の噴射条件（圧力０．０８～０．１３ＭＰａ、水量６６０±６０ｍｌ／分、噴射時間１２分／６０分照射、水温１６±５℃）、相対湿度５０±５％、試料面放射照度６０±３Ｗ／ｍ２（３００～４００ｎｍ）、１８０±３Ｗ／ｍ２（３００～４００ｎｍ）。
△Ｅ＝［（△Ｌ＊）２＋（△ａ＊）２＋（△ｂ＊）２］１／２
○・・・△Ｅ≦１．０
×・・・１．０＜△Ｅ 〔Weatherability〕
The same evaluation sample as that prepared in the section [Hue evaluation] was used. Initial values (L * , a * , b * ) were measured in the same manner as in the hue measurement method. Thereafter, L * , a * , and b * were measured after 300 hours in the weather resistance evaluation according to JIS D 0205, and ΔE was calculated by the following equation.
The weather resistance was evaluated using a low temperature xenon weather meter XL-75 manufactured by Suga Test Instruments Co., Ltd. The conditions are black panel temperature 63 ± 3 ° C, water injection conditions (pressure 0.08 to 0.13MPa, water amount 660 ± 60ml / min, injection time 12 minutes / 60 minutes, water temperature 16 ± 5 ° C), relative humidity 50 ± 5%, sample surface irradiance 60 ± 3 W / m 2 (300 to 400 nm), 180 ± 3 W / m 2 (300 to 400 nm).
ΔE = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ] 1/2
○ ・ ・ ・ △ E ≦ 1.0
× ・ ・ ・ 1.0 <△ E
〔耐環境性（色相変化△Ｅ）評価〕
〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。初期値（Ｌ＊、ａ＊、ｂ＊）を色相測定方法と同様に測定した。その後、試験サンプルを湿熱器に立てた状態で放置した。条件は、温度８５℃、湿度８５％、時間５００ｈｒとした。その後、常温に２４ｈｒ放置した後の試験後のＬ＊、ａ＊、ｂ＊を測定し、次式により△Ｅを算出した。
△Ｅ＝［（△Ｌ＊）２＋（△ａ＊）２＋（△ｂ＊）２］１／２
○・・・△Ｅ≦１．０
×・・・１．０＜△Ｅ [Evaluation of environmental resistance (hue change ΔE)]
The same evaluation sample as that prepared in the section [Hue evaluation] was used. Initial values (L * , a * , b * ) were measured in the same manner as in the hue measurement method. Then, the test sample was left standing in a state of standing on a moist heater. The conditions were a temperature of 85 ° C., a humidity of 85%, and a time of 500 hr. Thereafter, L * , a * , and b * after the test after being left at room temperature for 24 hours were measured, and ΔE was calculated by the following equation.
ΔE = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ] 1/2
○ ・ ・ ・ △ E ≦ 1.0
× ・ ・ ・ 1.0 <△ E
〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。初期値（Ｌ＊、ａ＊、ｂ＊）を色相測定方法と同様に測定した。その後、試験サンプルを湿熱器に立てた状態で放置した。条件は、温度８５℃、湿度８５％、時間５００ｈｒとした。その後、常温に２４ｈｒ放置した後の試験後のＬ＊、ａ＊、ｂ＊を測定し、次式により△Ｅを算出した。
△Ｅ＝［（△Ｌ＊）２＋（△ａ＊）２＋（△ｂ＊）２］１／２
○・・・△Ｅ≦１．０
×・・・１．０＜△Ｅ [Evaluation of environmental resistance (hue change ΔE)]
The same evaluation sample as that prepared in the section [Hue evaluation] was used. Initial values (L * , a * , b * ) were measured in the same manner as in the hue measurement method. Then, the test sample was left standing in a state of standing on a moist heater. The conditions were a temperature of 85 ° C., a humidity of 85%, and a time of 500 hr. Thereafter, L * , a * , and b * after the test after being left at room temperature for 24 hours were measured, and ΔE was calculated by the following equation.
ΔE = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ] 1/2
○ ・ ・ ・ △ E ≦ 1.0
× ・ ・ ・ 1.0 <△ E
〔耐環境性評価〕
サイズを１０ｃｍとする以外は、〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。サンプルを湿熱器に立てた状態で放置した。条件は、温度８５℃、湿度８５％、時間５００ｈｒとした。その後、常温に２４ｈｒ放置した後の外観を観察して評価した。
○・・・剥離、発泡の発生なし。
×・・・剥離、発泡の発生あり。 (Environmental resistance evaluation)
Except that the size was 10 cm, the same sample as the evaluation sample prepared in the section of [Hue evaluation] was used. The sample was left standing on a wet heat. The conditions were a temperature of 85 ° C., a humidity of 85%, and a time of 500 hr. Thereafter, the appearance after standing at room temperature for 24 hours was observed and evaluated.
・ ・ ・: No peeling or foaming occurred.
×: peeling and foaming occurred.
サイズを１０ｃｍとする以外は、〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。サンプルを湿熱器に立てた状態で放置した。条件は、温度８５℃、湿度８５％、時間５００ｈｒとした。その後、常温に２４ｈｒ放置した後の外観を観察して評価した。
○・・・剥離、発泡の発生なし。
×・・・剥離、発泡の発生あり。 (Environmental resistance evaluation)
Except that the size was 10 cm, the same sample as the evaluation sample prepared in the section of [Hue evaluation] was used. The sample was left standing on a wet heat. The conditions were a temperature of 85 ° C., a humidity of 85%, and a time of 500 hr. Thereafter, the appearance after standing at room temperature for 24 hours was observed and evaluated.
・ ・ ・: No peeling or foaming occurred.
×: peeling and foaming occurred.
各物性の評価結果を表１～表４に示す。
Tables 1 to 4 show the evaluation results of each physical property.
〔顔料粒径〕
〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。サンプルの５ｍｍ２のエリアを光学顕微鏡にて観察し、倍率１５００倍にて顔料粒径を測定した。実施例１のサンプルは顔料の最大粒径が５．０μｍ以下であるのに対し、実施例１５のサンプルは顔料の最大粒径が５．０μｍを超える結果となった。観察エリア中で、大きさが目立つ粒径の代表的な測定結果を表５に示す。 (Pigment particle size)
The same evaluation sample as that prepared in the section [Hue evaluation] was used. A 5 mm 2 area of the sample was observed with an optical microscope, and the pigment particle size was measured at a magnification of 1500 times. In the sample of Example 1, the maximum particle size of the pigment was 5.0 μm or less, whereas in the sample of Example 15, the maximum particle size of the pigment exceeded 5.0 μm. Table 5 shows a typical measurement result of the particle size in which the size is conspicuous in the observation area.
〔色相評価〕の項で作製した評価用サンプルと同様のものを用いた。サンプルの５ｍｍ２のエリアを光学顕微鏡にて観察し、倍率１５００倍にて顔料粒径を測定した。実施例１のサンプルは顔料の最大粒径が５．０μｍ以下であるのに対し、実施例１５のサンプルは顔料の最大粒径が５．０μｍを超える結果となった。観察エリア中で、大きさが目立つ粒径の代表的な測定結果を表５に示す。 (Pigment particle size)
The same evaluation sample as that prepared in the section [Hue evaluation] was used. A 5 mm 2 area of the sample was observed with an optical microscope, and the pigment particle size was measured at a magnification of 1500 times. In the sample of Example 1, the maximum particle size of the pigment was 5.0 μm or less, whereas in the sample of Example 15, the maximum particle size of the pigment exceeded 5.0 μm. Table 5 shows a typical measurement result of the particle size in which the size is conspicuous in the observation area.
本出願は、２０１８年７月３１日に日本国特許庁へ出願された日本特許出願（特願２０１８－１４４３７３）に基づくものであり、その内容はここに参照として取り込まれる。
This application is based on Japanese Patent Application (No. 2018-144373) filed with the Japan Patent Office on July 31, 2018, the contents of which are incorporated herein by reference.
本発明の接着剤は、タッチスクリーンパネル等のディスプレイ貼付用接着剤としての産業上利用可能性を有する。
The adhesive of the present invention has industrial applicability as an adhesive for attaching a display such as a touch screen panel.
The adhesive of the present invention has industrial applicability as an adhesive for attaching a display such as a touch screen panel.
Claims (5)
- 光硬化性を有するディスプレイ貼付用接着剤であって、
赤色顔料、青色顔料、及び黄色顔料を含有する色材を含み、光硬化後における、ＣＩＥ Ｌａｂ色空間表示系におけるａ＊及びｂ＊が、それぞれ、－３．０≦ａ＊≦３．０、－３．０≦ｂ＊≦３．０を満たすディスプレイ貼付用接着剤。 An adhesive for applying a display having photocurability,
A * and b * in the CIE Lab color space display system after photocuring, including a color material containing a red pigment, a blue pigment, and a yellow pigment, are respectively -3.0 ≦ a * ≦ 3.0; -Adhesive for attaching a display that satisfies -3.0≤b * ≤3.0. - ＵＶ硬化型プレポリマー及び光重合開始剤を更に含む請求項１記載のディスプレイ貼付用接着剤。 2. The adhesive for attaching a display according to claim 1, further comprising a UV curable prepolymer and a photopolymerization initiator.
- （メタ）アクリル系シランカップリング剤を更に含む請求項１又は２記載のディスプレイ貼付用接着剤。 3. The adhesive according to claim 1, further comprising a (meth) acrylic silane coupling agent.
- 光硬化後において、ヘイズが５．０％以下である請求項１～３のいずれか１項に記載のディスプレイ貼付用接着剤。 (4) The adhesive for pasting a display according to any one of (1) to (3), which has a haze of 5.0% or less after light curing.
- ５ｍｍ２当たりの光学顕微鏡像において、５．０μｍ以上である色材の二次粒子が実質的に存在しない請求項１～４のいずれか１項に記載のディスプレイ貼付用接着剤。 5. The adhesive according to claim 1, wherein substantially no secondary particles of the coloring material having a size of 5.0 μm or more are present in an optical microscope image per 5 mm 2 .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018144373 | 2018-07-31 | ||
| JP2018-144373 | 2018-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020026955A1 true WO2020026955A1 (en) | 2020-02-06 |
Family
ID=69232449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2019/029315 WO2020026955A1 (en) | 2018-07-31 | 2019-07-25 | Adhesive for application to display |
Country Status (2)
| Country | Link |
|---|---|
| TW (1) | TW202018041A (en) |
| WO (1) | WO2020026955A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113950631A (en) * | 2020-03-04 | 2022-01-18 | 株式会社Lg化学 | Optical film and display device including the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000265133A (en) * | 1999-03-11 | 2000-09-26 | Tomoegawa Paper Co Ltd | Application film for electronic display |
| JP2002297046A (en) * | 2001-03-30 | 2002-10-09 | Arisawa Mfg Co Ltd | Sticking film for electronic display |
| WO2014069542A1 (en) * | 2012-10-30 | 2014-05-08 | 旭硝子株式会社 | Laminated body and display device |
| WO2015015962A1 (en) * | 2013-08-01 | 2015-02-05 | Dic株式会社 | Pigment composition for color filter and color filter |
-
2019
- 2019-07-25 WO PCT/JP2019/029315 patent/WO2020026955A1/en active Application Filing
- 2019-07-30 TW TW108127027A patent/TW202018041A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000265133A (en) * | 1999-03-11 | 2000-09-26 | Tomoegawa Paper Co Ltd | Application film for electronic display |
| JP2002297046A (en) * | 2001-03-30 | 2002-10-09 | Arisawa Mfg Co Ltd | Sticking film for electronic display |
| WO2014069542A1 (en) * | 2012-10-30 | 2014-05-08 | 旭硝子株式会社 | Laminated body and display device |
| WO2015015962A1 (en) * | 2013-08-01 | 2015-02-05 | Dic株式会社 | Pigment composition for color filter and color filter |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113950631A (en) * | 2020-03-04 | 2022-01-18 | 株式会社Lg化学 | Optical film and display device including the same |
| JP2022534874A (en) * | 2020-03-04 | 2022-08-04 | エルジー・ケム・リミテッド | OPTICAL FILM AND DISPLAY DEVICE INCLUDING THE SAME |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202018041A (en) | 2020-05-16 |
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