CN107722916B - UV-curable resin composition - Google Patents

UV-curable resin composition Download PDF

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Publication number
CN107722916B
CN107722916B CN201710576642.XA CN201710576642A CN107722916B CN 107722916 B CN107722916 B CN 107722916B CN 201710576642 A CN201710576642 A CN 201710576642A CN 107722916 B CN107722916 B CN 107722916B
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Prior art keywords
resin composition
meth
mass
component
curable resin
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CN107722916A (en
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佐藤信之
福田裕美
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Arisawa Mfg Co Ltd
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Arisawa Mfg Co Ltd
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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Abstract

The present invention relates to a UV curable resin composition. The present invention addresses the problem of providing a UV-curable resin composition that can be easily peeled off from an adherend to regenerate an LCD even at room temperature and can impart good adhesion, and an adhesive sheet comprising the same. The solution of the present invention is a UV-curable resin composition comprising (A) a UV-curable prepolymer, (B) a UV-curable polyfunctional monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent, wherein the component (A) is urethane (meth) acrylate, the content of the component (B) is 15 to 60 parts by mass, the content of the component (C) is 0.5 parts by mass or more, and the content of the component (D) is 0.1 to 5 parts by mass, based on 100 parts by mass of the component (A).

Description

UV-curable resin composition
Technical Field
The present invention relates to a UV curable resin composition useful for a display portion of a liquid crystal display and an adhesive sheet comprising the same.
Background
Currently, with the spread of digital electronic devices, Liquid Crystal Displays (LCDs) have become quite common display devices, and are used as display portions of various devices such as liquid crystal televisions or PC displays, portable telephone terminals, portable game machines, desktop calculators, clocks, and the like. In particular, in recent years, there is a liquid crystal display in which a patterned retardation plate (patterning plate) made of glass is bonded to an LCD for the purpose of providing a 3D function.
Here, the LCD to which the retardation plate is bonded may be recovered after use, and only the LCD may be reused. For example, it is being required to peel off the phase difference plate from the LCD to reproduce the LCD (rework). In this case, a conventional method is adopted in which the entire LCD is cooled (in other words, the adhesive is cooled) and the retardation plate is peeled off from the LCD. However, in this method, equipment for cooling is necessary, and workability is not good. Further, since both the retardation plate and the LCD have rigidity, there is a problem that either one is broken when peeling off. That is, in the conventional adhesive sheet, after the LCD and the retardation plate are adhered, the LCD is easily peeled off and the LCD is difficult to be reproduced.
In order to solve the above-described problems, an adhesive sheet has been studied which can be easily peeled off even when the temperature is normal and the adherend is a hard material such as glass. For example, patent document 1 proposes a transparent adhesive film containing an adhesive component and a gas generating agent that generates gas by irradiation with ultraviolet rays. Further, patent document 2 proposes a heat-and actinic-ray-curable (photocurable) adhesive composition.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-56244
Patent document 2: japanese Kohyo publication 2011-508814
Disclosure of Invention
Problems to be solved by the invention
However, the transparent adhesive film described in patent document 1 requires exposure during recycling, and the actinic ray-curable (photocurable) adhesive composition described in patent document 2 removes the adhesive by heating and cutting the adhesive with a thread (wire) during recycling. That is, the following situation exists: an adhesive sheet which not only ensures good adhesion but also enables easy peeling of an LCD from an adherend at room temperature has not been obtained so far.
In view of the above circumstances, an object of the present invention is to provide a UV-curable resin composition which can easily peel an LCD from an adherend and regenerate the LCD even at room temperature and can impart good adhesiveness, and an adhesive sheet comprising the same.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a UV-curable resin composition containing (a) a urethane (meth) acrylate (urethane) component, (B) a UV-curable polyfunctional monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent, wherein the content of the (B) component is 15 to 60 parts by mass, the content of the (C) component is 0.5 parts by mass or more, and the content of the (D) component is 0.1 to 5 parts by mass, based on 100 parts by mass of the (a) component, can solve the above problems, and have completed the present invention.
Namely, the present invention is as follows.
[1]
A UV-curable resin composition comprising (A) a UV-curable prepolymer, (B) a UV-curable polyfunctional monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent,
the component (A) is urethane (meth) acrylate,
the content of the component (B) is 15 to 60 parts by mass, the content of the component (C) is 0.5 parts by mass or more, and the content of the component (D) is 0.1 to 5 parts by mass, based on 100 parts by mass of the component (A).
[2]
The UV-curable resin composition according to [1], wherein the urethane (meth) acrylate is at least 1 selected from the group consisting of a urethane (meth) acrylate having a polycarbonate skeleton, a urethane (meth) acrylate having a polyether skeleton, and a urethane (meth) acrylate having a polyester skeleton.
[3]
The UV-curable resin composition according to [1] or [2], wherein the urethane (meth) acrylate has a weight average molecular weight of 10,000 to 100,000 and a double bond equivalent of 1,000 to 5,000 g/eq.
[4]
The UV-curable resin composition according to any one of the above [1] to [3], wherein the (B) UV-curable polyfunctional monomer is a (meth) acrylic monomer having 2 or more functional groups.
[5]
The UV-curable resin composition according to any one of the above [1] to [4], wherein the photopolymerization initiator (C) is an acylphosphine oxide-based photopolymerization initiator.
[6]
The UV-curable resin composition according to [5], wherein the acylphosphine oxide photopolymerization initiator is 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.
[7]
The UV-curable resin composition according to any one of the above [1] to [6], wherein the (D) silane coupling agent is a silane coupling agent having a (meth) acrylic group.
[8]
An adhesive sheet comprising the UV-curable resin composition according to any one of [1] to [7 ].
[9]
The adhesive sheet according to [8], wherein a dried film thickness of the adhesive sheet is 10 to 250 μm.
[10]
A 3D liquid crystal panel formed by laminating an LCD and a pattern phase difference plate, wherein,
and bonding the LCD and the phase difference plate with the bonding sheet described in [8] or [9 ].
[11]
The 3D liquid crystal panel according to item [10], wherein the pattern phase difference plate is a glass plate formed with a pattern.
ADVANTAGEOUS EFFECTS OF INVENTION
The adhesive sheet comprising the UV curable resin composition of the present invention can easily peel the LCD from the adherend and regenerate the LCD even at room temperature, and can impart good adhesion.
Detailed Description
Hereinafter, specific embodiments of 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 various modifications can be made within the scope of the present invention.
In the UV-curable resin composition of the present embodiment,
comprising (A) a UV-curable prepolymer, (B) a UV-curable polyfunctional monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent,
the component (A) is urethane (meth) acrylate,
the content of the component (B) is 15 to 60 parts by mass, the content of the component (C) is 0.5 parts by mass or more, and the content of the component (D) is 0.1 to 5 parts by mass, based on 100 parts by mass of the component (A).
[ (A) UV-curable prepolymer ]
The UV-curable resin composition of the present embodiment contains (a) a UV-curable prepolymer (hereinafter, also referred to as "component (a)"). The UV curable prepolymer is not particularly limited as long as it is a urethane (meth) acrylate having a urethane structure in the main chain and a (meth) acrylic group in the side chain. The urethane (meth) acrylate is not particularly limited, and examples thereof include urethane (meth) acrylates having a polycarbonate skeleton, urethane (meth) acrylates having a polyether skeleton, urethane (meth) acrylates having a polyester skeleton, and the like, and among them, urethane (meth) acrylates having a polycarbonate skeleton are preferable from the viewpoint of no yellowing of the cured adhesive sheet.
The urethane (meth) acrylate having a polycarbonate skeleton is a prepolymer having a polycarbonate structure and a urethane structure in the main chain and having a (meth) acrylic group in the side chain. Urethane (meth) acrylates having a polycarbonate skeleton can be obtained, for example, by: polycarbonate diol, diisocyanate, and carboxylic acid diol are reacted, and then reacted with glycidyl (meth) acrylate.
The polycarbonate diol preferably has a weight average molecular weight of 170 to 1,000, more preferably 300 to 700, and further preferably 400 to 600. When the weight average molecular weight of the polycarbonate diol is in the above range, the film properties necessary for the regeneration tend to be imparted to the urethane prepolymer main chain.
The diisocyanate is not particularly limited, and examples thereof include aromatic isocyanates such as 2, 4-tolylene diisocyanate (2,4-TDI), 2, 6-tolylene diisocyanate (2,6-TDI), 4 '-diphenylmethane diisocyanate (4, 4' -MDI), 2,4 '-diphenylmethane diisocyanate (2, 4' -MDI), 1, 4-phenylene diisocyanate, Xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), dimethylbiphenyl diisocyanate (TODI, tolidine diisocyanate), and 1, 5-Naphthalene Diisocyanate (NDI); aliphatic polyisocyanates such as Hexamethylene Diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), and the like; and alicyclic polyisocyanates such as trans-1, 4-cyclohexyl diisocyanate, isophorone diisocyanate (IPDI), and H6XDI (hydrogenated XDI), among which hexamethylene diisocyanate is preferable from the viewpoint of optical characteristics (yellowing is less likely to occur).
The carboxylic acid diol is not particularly limited, and examples thereof include dimethylolbutanoic acid and dimethylolpropanoic acid.
The urethane (meth) acrylate having a polyether skeleton is a prepolymer having a polyether structure and a urethane structure in the main chain and having a (meth) acrylic group in the side chain; the urethane (meth) acrylate having a polyester skeleton is a prepolymer having a polyester structure and a urethane structure in the main chain and having a (meth) acrylic group in the side chain. The prepolymer can be obtained by the same method as that for the urethane (meth) acrylate having a polycarbonate skeleton, except that a polyether diol or a polyester diol is used instead of the polycarbonate diol. In this case, the preferred weight average molecular weight of the polyether diol or the polyester diol is the same as that of the polycarbonate diol.
(A) The weight average molecular weight of the component (A) is preferably 10,000 to 100,000, more preferably 30,000 to 70,000, and still more preferably 40,000 to 60,000. When the weight average molecular weight is in the above range, film formability and curability tend to be good, and long-term reliability tends to be good.
Here, the weight average molecular weight is a value measured by Gel Permeation Chromatography (GPC) using standard polystyrene having an average molecular weight of about 500 to about 100 ten thousand.
(A) The equivalent of the double bond of the component (A) is preferably 1,000 to 5,000g/eq, more preferably 1,500 to 2,500g/eq, and still more preferably 1,800 to 2,200 g/eq. When the double bond equivalent is in the above range, the effect of curing shrinkage is small, long-term reliability is excellent, and curing and regeneration tend to be easy.
Here, the double bond equivalent is a value calculated from the mass (g)/(the number of moles of the compound having an oxirane ring and an ethylenically unsaturated bond) (g/mol) of the solid content of the carboxyl group-containing (meth) acrylate.
(A) The glass transition temperature (Tg) of the component (B) is preferably-10 to 20 ℃, more preferably-5 to 15 ℃, and still more preferably 0 to 10 ℃. When the glass transition temperature is in the above range, the long-term reliability and the reproducibility tend to be well balanced.
Here, the glass transition temperature is a value measured by dynamic viscoelasticity measurement (DMA).
[ (B) UV-curable polyfunctional monomer ]
The UV-curable resin composition of the present embodiment contains (B) a UV-curable polyfunctional monomer (hereinafter, also referred to as "component (B)"). In order to make the LCD renewable, it is necessary toIn the present embodiment, the UV curable polyfunctional monomer is added to the UV curable prepolymer, thereby increasing the crosslinking density after curing, and thus increasing the viscoelasticity at room temperature. Here, the viscoelasticity of the UV-curable resin composition can be measured by dynamic viscoelasticity measurement (DMA), and the storage elastic modulus at normal temperature (25 ℃) after curing is preferably 1.0X 108～1.0×1010Pa, more preferably 4.0X 108～5.0×109Pa, more preferably 6.0X 108～3.0×109Pa。
The component (B) is not particularly limited, and examples thereof include (meth) acrylic monomers, and among them, (meth) acrylic monomers having 2 or more functional groups are preferable from the viewpoint of increasing the crosslinking density and improving the reproducibility.
Specific examples of the component (B) having 2 functional groups include 1, 4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, tricyclodecane dimethanol diacrylate; examples of the component (B) having 3 functional groups include trimethylolpropane triacrylate, trimethylolmethane tri (meth) acrylate, trimethylolpropane propylene oxide (trimethyolpropane propylene oxide) -modified tri (meth) acrylate; examples of the component (B) having 4 or more functional groups include dipentaerythritol tetra (meth) acrylate, pentaerythritol oxirane-modified tetra (meth) acrylate, pentaerythritol oxirane-modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, etc., and among them, from the viewpoint of recyclability, a (meth) acrylic monomer having 4 or more functional groups is preferable, and dipentaerythritol hexaacrylate having 6 functional groups is more preferable.
The content of the component (B) is 15 to 60 parts by mass, preferably 18 to 40 parts by mass, and more preferably 20 to 30 parts by mass, per 100 parts by mass of the component (A). If the content of the component (B) is less than 15 parts by mass, the adhesiveness after curing is high, and the recyclability at room temperature is deteriorated, and if it exceeds 60 parts by mass, the adhesiveness is insufficient, and the long-term reliability is deteriorated. When the content of the component (B) is adjusted to be within the above range with respect to 100 parts by mass of the component (a), the melt viscosity of the resin composition is maintained within a certain range, and thus, there is an advantage that uneven sticking and image disturbance are less likely to occur.
[ (C) photopolymerization initiator ]
The UV curable resin composition of the present embodiment contains (C) a photopolymerization initiator (hereinafter, also referred to as "component (C)"). The photopolymerization initiator is not particularly limited, and any photopolymerization initiator such as an acylphosphine oxide photopolymerization initiator, an alkylphenone photopolymerization initiator, and an intramolecular hydrogen abstraction photopolymerization initiator can be used, and among them, an acylphosphine oxide photopolymerization initiator is preferable from the viewpoint of reactivity and curing uniformity. Specific examples thereof include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-dimethoxy-1, 2-diphenylethan-1-one, and phenylglyoxalic acid methyl ester, among which 2,4, 6-trimethylbenzoyldiphenylphosphine oxide is preferable from the viewpoint of high radical generation efficiency and deep curing property.
The content of the component (C) is 0.5 parts by mass or more, preferably 1.0 parts by mass or more, and more preferably 1.5 parts by mass or more, relative to 100 parts by mass of the component (a). When the content of the photopolymerization initiator (C) is in the above range, the curing reactivity tends to be good, and the reproducibility and long-term reliability tend to be improved. The upper limit of the content of the component (C) is not particularly limited, but is preferably 7.0 parts by mass or less because an excessive amount tends to lower the optical properties.
[ (D) silane coupling agent ]
The UV curable resin composition of the present embodiment contains (D) a silane coupling agent (hereinafter, also referred to as "component (D)") in addition to the components (a) to (C) described above. As described above, the UV-curable resin composition of the present embodiment includes the UV-curable polyfunctional monomer, thereby improving viscoelasticity at normal temperature and enabling LCD recycling. On the other hand, when the viscoelasticity is high, the adhesiveness to the adherend tends to be lowered. In the present embodiment, the silane coupling agent is contained in the UV curable resin composition, whereby long-term reliability is improved particularly when the adherend is a glass plate while maintaining the adhesive strength.
The component (D) is not particularly limited, and may be any silane coupling agent such as a monomeric silane coupling agent, an alkoxyoligomer silane coupling agent, or a polyfunctional silane coupling agent. Among these, from the viewpoint of improving the adhesion when the adherend is glass and maintaining the long-term reliability, a silane coupling agent having a (meth) acrylic group is preferable, and 3-acryloxypropyltrimethoxysilane is more preferable.
The content of the component (D) is 0.1 to 5 parts by mass, preferably 0.5 to 3.0 parts by mass, and more preferably 0.5 to 1.5 parts by mass, relative to 100 parts by mass of the component (A). When the content of the component (D) is in the above range, the balance between the long-term reliability and the reproducibility tends to be good.
[ other ingredients ]
The UV curable resin composition of the present embodiment may contain various fillers such as silica, alumina, hydrated alumina, etc. in addition to the above components (a) to (D); an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a leveling agent (leveling agent), an antifoaming agent, a coloring pigment, an organic solvent, and the like are additives that are generally added to the adhesive.
[ adhesive sheet ]
The adhesive sheet in the present embodiment contains the above-described UV-curable resin composition. Specifically, for example, an adhesive sheet having protective films on both sides can be obtained by applying a resin composition to a protective film such as PET, drying the resin composition, and then providing a protective film on the opposite side. Particularly preferably, the UV-curable resin composition is formed into a varnish using an organic solvent, and then coated on a protective film and dried. The organic solvent used in this case is not particularly limited, and examples thereof include toluene, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide. Among them, methyl ethyl ketone is preferable from the viewpoint of solubility. The content of the organic solvent in the varnish is preferably 30 to 90 parts by mass, and more preferably 40 to 70 parts by mass, based on 100 parts by mass of the component (a).
The protective film is not particularly limited, and examples thereof include films formed of 1 or more kinds of resins selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, and among these, films formed of polyethylene terephthalate resins are preferable from the viewpoint of reducing the production cost.
The surface of the protective film to which the resin composition is applied may be subjected to a mold release treatment. By subjecting the protective film to a mold release treatment, the protective film can be easily peeled off at the time of use, and therefore, the workability is improved. The release treatment is not particularly limited, and examples thereof include a release agent such as a silicone release agent, a fluorine release agent, and a long-chain alkyl graft polymer release agent, and a method of performing a surface treatment by plasma treatment.
As a method for coating the UV curable resin composition on the protective film, a comma coater (comma coater), a die coater (die coater), a gravure coater, or the like can be suitably used depending on the coating thickness.
The drying of the UV curable resin composition may be carried out using an in-line dryer (in-line dryer), and the drying conditions in this case may be appropriately adjusted depending on the kinds and amounts of the respective components. The thickness of the dried adhesive sheet is preferably 10 to 250 μm, more preferably 25 to 125 μm, and still more preferably 30 to 75 μm. When the thickness of the adhesive sheet is in the above range, the adhesiveness is good, and the long-term reliability is improved. In the present embodiment, the long-term reliability specifically includes the following cases: since the adhesion between the LCD and the pattern phase difference plate is good, the misalignment is not likely to occur, and as a result, the observer can observe a good 3D image. Further, if the thickness of the adhesive sheet is in the above range, the distance between the LCD and the pattern retardation plate becomes appropriate, and an appropriate viewing angle can be secured when viewing 3D images.
[3D liquid Crystal Panel ]
The 3D liquid crystal panel according to the present embodiment is formed by laminating an LCD and a pattern retardation plate, and the LCD and the retardation plate are bonded by the adhesive sheet according to the present embodiment. The 3D liquid crystal panel can be obtained, for example, by: an adhesive sheet is bonded to the retardation plate, an LCD is bonded from above, and the adhesive sheet is UV-cured by UV irradiation.
As the pattern phase difference plate, a glass plate having a pattern formed thereon can be used.
The UV curable resin composition of the present embodiment can be used not only for 3D liquid crystal panels but also for all applications where display devices such as LCDs and organic ELs are desired to be reproduced. Examples of such applications include touch sensor panels and digital signage (digital signage).
Examples
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.
The components and materials used in the examples and comparative examples are as follows.
[ (A) ingredient: UV-curable prepolymer
UV-curable prepolymers (a) to (d) were prepared according to the following synthetic examples 1 to 3 and comparative synthetic example 1.
[ (B) ingredient: UV-curable polyfunctional monomer
(1) UV-curable polyfunctional monomer (a)
Dipentaerythritol hexaacrylate
Manufactured by Daicel-Allnex Ltd, product name "DPHA"
(2) UV-curable polyfunctional monomer (b)
Dicyclodecane dimethanol diacrylate
Manufactured by Daicel-Allnex Ltd, product name "IRR 214-K"
(3) UV-curable polyfunctional monomer (c)
Trimethylolpropane triacrylate
Product name "TMPTA" manufactured by Daicel-Allnex Ltd "
(4) UV-curable polyfunctional monomer (d)
Ethoxylated phenyl acrylates (monofunctional)
Product name "EBECRYL 110" manufactured by Daicel-Allnex Ltd "
[ (C) ingredient: photopolymerization initiator
(1) Photopolymerization initiator (a)
2,4, 6-trimethylbenzoyldiphenylphosphine oxide
Irgacure TPO, trade name of BASF corporation, acylphosphine oxide-based photopolymerization initiator
(2) Photopolymerization initiator (b)
2, 2-dimethoxy-1, 2-diphenylethan-1-one
Product name "Irgacure 651" manufactured by BASF corporation, alkylphenone-based photopolymerization initiator
(3) Photopolymerization initiator (c)
Phenylglyoxylic acid methyl ester
An intramolecular hydrogen abstraction-type photopolymerization initiator manufactured by BASF corporation under the trade name of Irgacure MBF
[ (D) ingredient: silane coupling agent
(1) Silane coupling agent (a)
Monomeric silane coupling agent
Trade name "KBM-5103", 3-acryloxypropyltrimethoxysilane, "products of shin-Etsu chemical industries, Ltd
(2) Silane coupling agent (b)
Alkoxy oligomer type silane coupling agent
Manufactured by shin-Etsu chemical industries, Inc., trade name "KR-513"
(3) Silane coupling agent (c)
Multifunctional silane coupling agent
Trade name "X-12-1050", manufactured by shin-Etsu chemical industries, Ltd "
The evaluation methods and the measurement methods are as follows.
[ reproducibility ]
(1) Sample preparation step
Will stick toThe PET film on one side of the sheet was peeled off, and the sheet was laminated on glass (0.7t, 19 inches) and subjected to a hot press (autoclave) treatment. The lamination is performed by roller lamination under the conditions that the temperature of a laminating roller is 25-40 ℃, the linear pressure of the laminating roller is 1.0-2.0 kgf/cm and the speed of the laminating roller is 0.3-2.0 m/min; the hot pressing was carried out at 60 ℃ under 0.6MPa for 10 min. The PET film on the other side was peeled off, attached to the LCD by vacuum lamination, again subjected to a heat press treatment, and then subjected to UV exposure to obtain a test sample. The vacuum lamination is carried out at a temperature of 25-50 deg.C and a pressure of 0.01-0.05 MPa for 60s under vacuum and 30s under pressure. The hot pressing is carried out at 60 deg.C and 0.6MPa for 1 hr. UV exposure was carried out using an ultra-high pressure mercury lamp light source so that the cumulative light amount became 3000mJ/cm2The method (2) is implemented.
(2) Measurement method
After the test sample was left at room temperature for 24 hours or more, the adherend (glass, LCD) from which the glass was peeled was observed for breakage, and evaluated according to the following criteria.
Very good: can be easily regenerated without damaging the adherend
O: can be regenerated without damaging the adherend
X: is difficult to regenerate
[ adhesiveness ]
(1) Sample preparation step
Test samples were prepared by the same procedure as for reproducibility.
(2) Measurement method
The test specimen was placed in a moist heat apparatus in an upright state. The conditions are 50 deg.C, 80% humidity, and 240 hr. Then, the mixture was left at room temperature for 24 hr. The presence or absence of displacement, floating, and foaming of the glass bonding position when compared with the time when the glass was placed in the moist heat apparatus was observed, and evaluated according to the following criteria.
O: no dislocation, floating and foaming of glass
X: the dislocation, floating and foaming of the glass are generated
[ Adaptation ]
(1) Sample preparation step
Test samples were prepared by the same procedure as for reproducibility.
(2) Measurement method
The display of the test sample was lighted and evaluated according to the following criteria.
O: display image without uneven sticking and 3D misalignment (without double image generation)
X: uneven sticking and 3D misalignment (double image generation) occurred in the display image
[ optical characteristics ]
(1) Sample preparation step
The PET film on one side of the adhesive sheet was peeled off, and the resultant was attached to an optical glass (40mm square) by vacuum lamination. The vacuum lamination is carried out at a temperature of 25 to 50 ℃, a pressure of 0.01 to 0.05MPa, a vacuum of 10s and a pressure of 10 s. The other PET film was peeled off, bonded to optical glass under the same conditions as the vacuum lamination, and then subjected to a hot press treatment and UV exposure to obtain a test sample. The hot pressing is carried out at 60 deg.C and 0.6MPa for 1 hr. UV exposure was carried out using an ultra-high pressure mercury lamp light source so that the cumulative light amount became 3000mJ/cm2The method (2) is implemented.
The Yellow Index (YI) of the test sample was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). The measurement conditions were: and C, a light source, transmission and wavelength lambda is 380-760 nm.
Very good: YI value less than 1.5
O: YI value of 1.5 or more and less than 2
X: YI value of 2 or more
Synthesis example 1 UV-curable prepolymer (a)
33.3 parts by mass of hexamethylene diisocyanate (HDI, trade name, manufactured by TOSOH CORPORATION), 59.4 parts by mass of polycarbonate diol having a weight average molecular weight of 400, 7.3 parts by mass of dimethylolbutyric acid, 1 part by mass of an organotin compound such as dibutyltin laurate (dibutyl tin laurate) as a catalyst, and 100 parts by mass of methyl ethyl ketone as an organic solvent were charged into a reaction vessel using a four-necked flask equipped with a thermometer, a condenser tube, and a stirring device, and reacted at 70 ℃ for 24 hours.
In order to confirm the reaction of the obtained composition, analysis was performed using an IR measuring instrument. The NCO characteristic absorption (2270 cm) of the composition in the IR chart was confirmed-1) Disappeared and it was confirmed that the composition was a carbamate having a carboxyl group.
Next, 100 parts by mass of the obtained carbamate having a carboxyl group, 7.1 parts by mass of glycidyl methacrylate, 0.7 part by mass of triethylamine as a catalyst, and 0.05 part by mass of hydroquinone as a polymerization inhibitor were added to a reaction vessel, and subjected to an addition reaction at 75 ℃ for 12 hours, thereby obtaining a UV curable prepolymer (a).
The addition reaction was terminated at a time point when the acid value was 5mgKOH/g or less as measured by the following method. The weight average molecular weight of the obtained UV curable prepolymer (a) was 50,000, the solid content concentration was 50% by mass, the double bond equivalent was 2,000g/eq, and the Tg was 5 ℃.
(method of measuring acid value)
1g of the solid content of the resin was weighed, a mixed solvent (mass ratio: toluene/methanol: 50/50) was added and dissolved, and then an appropriate amount of phenolphthalein solution was added as an indicator, and the mixture was titrated with a 0.1N potassium hydroxide aqueous solution, and the acid value was measured by the following formula (. alpha.).
x＝10×Vf×56.1/(Wp×I)…(α)
(in the formula (. alpha.), x represents an acid value (mgKOH/g), Vf represents a titration amount (mL) of a 0.1N KOH aqueous solution, Wp represents a measured mass (g) of the resin solution, and I represents a measured proportion (mass%) of nonvolatile components in the resin solution.)
(Synthesis example 2) UV-curable prepolymer (b)
A UV curable prepolymer (b) was obtained in the same manner as in synthesis example 1, except that a polyether diol was used instead of the polycarbonate diol.
(Synthesis example 3) UV-curable prepolymer (c)
A UV curable prepolymer (c) was obtained in the same manner as in synthesis example 1, except that a polyester diol was used instead of the polycarbonate diol.
Comparative Synthesis example 1 UV-curable prepolymer (d)
100.0g of methoxypropanol (propylene glycol monomethyl ether (PGM)) as a polymerization solvent was charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised to 80 ℃ while stirring the mixture under a nitrogen stream. The following substances were added dropwise from a dropping funnel to the reaction vessel while keeping the temperature at 80 ℃ for 3 hours: 13.5 parts by mass of styrene, 67 parts by mass of ethyl acrylate, 11.5 parts by mass of acrylic acid, and 0.5g of azobisisobutyronitrile as a radical polymerization initiator, which were mixed in advance at room temperature. After the end of the dropwise addition, the reaction solution was heated to 90 ℃ while being stirred, and further stirred for 2 hours while keeping the temperature of the reaction solution at 90 ℃, thereby obtaining a copolymer.
Next, 100 parts by mass of the obtained copolymer, 7.8 parts by mass of glycidyl methacrylate, 0.8 part by mass of triethylamine as a catalyst, and 0.05 part by mass of hydroquinone as a polymerization inhibitor were charged into a reaction vessel, and subjected to an addition reaction at 100 ℃ for 12 hours to obtain a UV curable prepolymer (d).
The addition reaction was terminated at a time point when the acid value became 5mgKOH/g or less. The weight average molecular weight of the obtained UV curable prepolymer (d) was 45,000, the solid content concentration was 47 mass%, and the Tg was 3 ℃.
(example 1)
(1) Preparation of UV-curable resin composition
To a reaction vessel, 100 parts by mass of the UV-curable prepolymer (a), 25 parts by mass of the UV-curable polyfunctional monomer (a), 1.5 parts by mass of the photopolymerization initiator (a), 1 part by mass of the silane coupling agent (a), and 140 parts by mass of methyl ethyl ketone as a solvent were added and stirred to obtain a resin composition.
(2) Production of adhesive sheet
The resin composition obtained in the above (1) was applied to a 38 μm PET film so that the thickness after drying was 30 μm or more, dried at 130 ℃ for 5 minutes, and then a PET film was provided also on the opposite side, to obtain an adhesive sheet having a PET film on both sides.
The obtained adhesive sheet was used to evaluate the recyclability, the adhesiveness, the bonding property and the optical properties.
Examples 2 to 20 and comparative examples 1 to 7
A UV curable resin composition and an adhesive sheet were obtained in the same manner as in example 1, except that the kinds and contents of the respective components were changed as described in tables 1 to 3.
The obtained adhesive sheet was used to evaluate the recyclability, the adhesiveness, the bonding property and the optical properties.
[ Table 1]
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9
UV-curable prepolymer (a) 100 100 100 100 100 100 100
UV-curable prepolymer (b) 100
UV-curable prepolymer (c) 100
UV-curable polyfunctional monomer (a) 25 25 25 60 15 25 25 25 25
Photopolymerization initiator (a) 1.5 1.5 1.5 1.5 1.5 0.5 5 1.5 1.5
Silane coupling agent (a) 1 1 1 1 1 1 1 0.1 5
Reproducibility of ◎ ◎ ◎ ◎ ○ ○ ◎ ◎ ○
Adhesion Property ○ ○ ○ ○ ○ ○ ○ ○ ○
Adhesive property ○ ○ ○ ○ ○ ○ ○ ○ ○
Optical characteristics ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎
[ Table 2]
Figure GDA0002749665930000171
[ Table 3]
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7
UV-curable prepolymer (a) 100 100 100 100 100 100
UV-curable prepolymer (d) 100
UV-curable polyfunctional monomer (a) 70 10 25 25 25 25
UV-curable polyfunctional monomer (d) 25
Photopolymerization initiator (a) 1.5 1.5 0.2 1.5 1.5 1.5 1.5
Photopolymerization initiator (b)
Photopolymerization initiator (c)
Silane coupling agent (a) 1 1 1 7 1 1
Reproducibility of ○ × × ◎ × ○ ×
Adhesion Property × ○ × × ○ × ○
Adhesive property × ○ ○ ○ ○ ○ ○
Optical characteristics ◎ ◎ ◎ ◎ ◎ ◎ ◎
Industrial applicability
An adhesive sheet comprising the UV curable resin composition of the present invention is industrially useful as an adhesive for liquid crystal displays and the like.

Claims (10)

  1. A UV-curable resin composition comprising (A) a UV-curable prepolymer, (B) a UV-curable polyfunctional monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent,
    the component (A) is urethane (meth) acrylate,
    the component (B) is a (meth) acrylic monomer having 2 or more (meth) acrylic groups,
    the content of the component (B) is 15 to 60 parts by mass, the content of the component (C) is 0.5 parts by mass or more, and the content of the component (D) is 0.1 to 5 parts by mass, based on 100 parts by mass of the component (A),
    the storage elastic modulus of the UV-curable resin composition at normal temperature, namely at 25 ℃ after curing is 6.0 x 108～1.0×1010Pa。
  2. 2. The UV-curable resin composition according to claim 1, wherein the urethane (meth) acrylate is at least 1 selected from the group consisting of a urethane (meth) acrylate having a polycarbonate skeleton, a urethane (meth) acrylate having a polyether skeleton, and a urethane (meth) acrylate having a polyester skeleton.
  3. 3. The UV-curable resin composition according to claim 1 or 2, wherein the urethane (meth) acrylate has a weight average molecular weight of 10,000 to 100,000 and a double bond equivalent of 1,000 to 5,000 g/eq.
  4. 4. The UV-curable resin composition according to claim 1 or 2, wherein the photopolymerization initiator (C) is an acylphosphine oxide-based photopolymerization initiator.
  5. 5. The UV-curable resin composition according to claim 4, wherein the acylphosphine oxide-based photopolymerization initiator is 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.
  6. 6. The UV-curable resin composition according to claim 1 or 2, wherein the (D) silane coupling agent is a silane coupling agent having a (meth) acrylic group.
  7. 7. An adhesive sheet comprising the UV-curable resin composition according to any one of claims 1 to 6.
  8. 8. The adhesive sheet according to claim 7, wherein the adhesive sheet has a dried film thickness of 10 to 250 μm.
  9. A9.3D liquid crystal panel, which is a 3D liquid crystal panel formed by laminating an LCD and a pattern phase difference plate, wherein,
    bonding the LCD and the phase difference plate using the adhesive sheet of claim 7 or 8.
  10. 10. The 3D liquid crystal panel of claim 9, wherein the pattern phase difference plate is a glass plate formed with a pattern.
CN201710576642.XA 2016-08-10 2017-07-14 UV-curable resin composition Active CN107722916B (en)

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