CN104231996A - LOCA (liquid optical clear adhesive) for full-attached module and preparation method of LOCA - Google Patents
LOCA (liquid optical clear adhesive) for full-attached module and preparation method of LOCA Download PDFInfo
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- CN104231996A CN104231996A CN201410481782.5A CN201410481782A CN104231996A CN 104231996 A CN104231996 A CN 104231996A CN 201410481782 A CN201410481782 A CN 201410481782A CN 104231996 A CN104231996 A CN 104231996A
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Abstract
The invention discloses an LOCA (liquid optical clear adhesive) for a full-attached module and a preparation method of the LOCA and belongs to the technical field of high polymer materials. The LOCA comprises substances in parts by weight as follows: 0-40 parts of polybutadiene-polyether block acrylic resin or polybutadiene-polyether block methacrylic resin, 0-30 parts of acrylic resin or methacrylic resin, 0-25 parts of an acrylic reactive diluent or a methacrylic reactive diluent, 0-30 parts of an inert plasticizer, 0-10 parts of a photoinitiator and 0-2 parts of an antioxidant. The LOCA is low in curing shrinkage rate, low in thermal stress, low in cured product modulus, good in flexibility and large in adhesive force, the deformation of a screen due to the stress can be avoided more easily when the LOCA is attached to an ultra-thin screen or a large-size screen, and production and usage requirements for the application to the full-attached module are completely met.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of Liquid optical clear adhesive for module of entirely fitting and preparation method thereof.
Background technology
Touch-control shows the trend that integrated module is current capacitive touch screen industry development, it has the advantages such as better display effect, simpler assembly technology, thinner thickness, has been widely used in the consumption electronic products such as mobile phone, panel computer, navigating instrument.Full coating technique is a kind of by touch module (Touch panel) with show the seamless applying technology of module (LCM).Full coating technique eliminates the clearance between screen, what contribute to reducing between display panel and glass is reflective, screen can be allowed to seem more penetrating, strengthen the display effect of screen, significantly reduce the thickness of screen simultaneously, effectively reduce the interference that display panel noise causes touch signal.
Mainly adopt at present and in two ways touch module and display module are fitted, i.e. optical transparent double-faced adhesive tape (OCA) and Liquid optical clear adhesive (LOCA), when using OCA to fit, there is the Contact of glue-line and bonding plane insufficient or be mixed into the problems such as bubble at binding face, especially, when the irregular surfaces such as curved surface, complicated surface, the shape face with difference of altitude are fitted, LOCA has better fillibility and simpler manufacturability.
But the module of the display such as LCM is in recent years more and more thinner.When using common LOCA to fit the different optical functional materialss such as frivolous LCM, TP, linear expansivity between differing materials there are differences, this species diversity easily causes screen in LOCA glue UV solidification process or produces dimensional change, warpage, display blackening equal stress concentration phenomenon when temperature, humidity change after solidification, screen size is larger, and this phenomenon is more obvious.Therefore develop and be applicable to full laminating, the LOCA that especially giant-screen is fitted entirely has great importance.And this kind of LOCA product being applicable to full laminating, also mainly concentrate on several transnational companys such as association is vertical, Henkel, domestic like product is also less, and the Liquid optical clear adhesive being applicable to full laminating of therefore developing high-quality just has more importantly meaning.
Volumetric shrinkage can not be excessive in the curing process for full laminating LOCA, and general requirement is less than 1%, and the LOCA volumetric shrinkage of the common G+G of being applicable to is generally 2%-3%; After solidification, hardness can not be excessive, and general requirement is less than 50 (Shore 00).Full laminating LOCA requires after the severe condition such as long high temperature resistant test, high-temp resisting high-humidity resisting test, cold-hot loop test, low temperature resistant test are aging, and its optical property and mechanical property are also very excellent, and property retention rate is more than 99%.
Summary of the invention
The object of the present invention is to provide a kind of Liquid optical clear adhesive for module of entirely fitting, there is excellent performance, lower shrinkage, low-stress, ageing-resistant advantage.
The present invention also aims to the preparation method that the above-mentioned Liquid optical clear adhesive for module of entirely fitting is provided.
A kind of Liquid optical clear adhesive for module of entirely fitting, be made up of the material of following parts by weight: polyhutadiene-polyether block acrylic resin or polyhutadiene-polyether block methacrylic resin 0 ~ 40 part, acrylic resin or methacrylic resin 0 ~ 30 part, vinylformic acid reactive thinner or methacrylic acid reactive thinner 0 ~ 25 part, inert plasticizer 0 ~ 30 part, light trigger 0 ~ 10 part, antioxidant 0 ~ 2 part.
The structural formula of described polyhutadiene-polyether block acrylic resin is as follows:
Wherein R represents 1, do not comprise the one in the part of isocyanate groups in hexamethylene-diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate molecular structure, R1 represents one in-H ,-CH3 or two kinds.
Described acrylic resin or methacrylic resin are the mixture of the one or more than one in epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, epoxy methacrylates, urethane methacrylate, polyester methacrylate, methacrylates and modifier thereof.
Described acrylic resin polyether acrylate.
Described vinylformic acid reactive thinner or methacrylic acid reactive thinner are one or more the mixture in isobornyl acrylate, isobornyl methacrylate, tetrahydrofuran (THF) acrylate, acrylic silicon ester, vinylformic acid Bian ester, lauric acid acrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, stearic acid acrylate, isodecyl acrylate.
Described inert plasticizer is one or more mixtures in polyether glycol, polyester polyol, liquid polybutadiene resin, liquid polyisoprene resin, dipropylene glycol dibenzoate, diethylene glycol dibenzoate, di-alcohol diacrylate, dibutylene glycol diacrylate.
Described light trigger is 2-hydroxy-methyl phenyl-propane-1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone, benzoin dimethylether, benzophenone, different monooctyl ester of contraposition N, N-dimethylaminobenzoic acid, 2; 4; 6-trimethylbenzoy-dipheny phosphine oxide, 2; one or more mixture in 4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester.
Described oxidation inhibitor is Hinered phenols antioxidant.
Described Hinered phenols antioxidant is antioxidant 1010.
For a preparation method for the Liquid optical clear adhesive of module of entirely fitting, it is characterized in that, above-mentioned various raw material is joined in clean planetary mixer according to described ratio successively, 2h is stirred under 50 DEG C of conditions, after vacuumizing and defoaming, naturally leave standstill to room temperature, to obtain final product.
Beneficial effect of the present invention: Liquid optical clear adhesive of the present invention, compared with the LOCA of general G+G purposes, has lower cure shrinkage, lower thermal stresses; Compared with the LOCA prepared with common polybutadiene-based polyurethane acrylate or hydrogenated butadiene polymer type polyurethane acrylate, after adding polyether block, the modulus of LOCA adhesive curing thing is lower, snappiness is better, when flatscreen laminating or the laminating of large size screen, more easily avoid the deformation that screen produces due to stress; Compared with the common full LOCA that fits, there is higher sticking power; Compared with the common full LOCA that fits, there is curing speed faster, the features such as lower solidification energy; This tackiness agent meets the production and application requirement being applied to full laminating module completely.
Polyhutadiene-polyether block (methyl) acrylic resin in the present composition is as the resin of this ultraviolet photo-curing LOCA, polybutadiene block imparts the good hydrophobicity of this LOCA adhesive curing thing, and this makes the moisture resistance properties of final touch-screen better; Polyether block imparts the good snappiness of this LOCA adhesive curing thing and lower modulus, this makes LOCA glue in the curing process, solidification internal stress can be absorbed greatly, flatscreen is avoided to produce the deformation such as warpage in LOCA solidification process, good snappiness and lower modulus also can in use due to the stress that temperature, humidity change produce, avoid flatscreen and produce the deformation such as warpage by absorbing screen greatly simultaneously.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1
A kind of Liquid optical clear adhesive for module of entirely fitting; be made up of the material of the parts by weight described in following table: polyhutadiene-polyether block acrylic resin I 15 parts; polyether acrylate 30 parts, Hydroxyethyl acrylate 5 parts, tetrahydrofuran (THF) acrylate 19.2 parts; dipropylene glycol dibenzoate 28 parts; 1-hydroxycyclohexyl phenyl ketone 2 parts, 2,4; 6-trimethylbenzoy-dipheny phosphine oxide 0.3 part, antioxidant 1010 0.3 part.
Described polyhutadiene-polyether block acrylic resin I structural formula is as shown in the formula (in formula m/n=1):
Above-mentioned various raw material is joined in clean planetary mixer successively according to described ratio, stirs 2h under 50 DEG C of conditions, after vacuumizing and defoaming, naturally leave standstill to room temperature, to obtain final product.
Embodiment 2
A kind of Liquid optical clear adhesive for module of entirely fitting; be made up of the material of the parts by weight described in following table: polyhutadiene-polyether block acrylic resin II 15 parts; urethane acrylate 30 parts, Hydroxyethyl acrylate 4 parts, tetrahydrofuran (THF) acrylate 22.2 parts; diethylene glycol dibenzoate 26 parts; 1-hydroxycyclohexyl phenyl ketone 5 parts, 2,4; 6-trimethylbenzoy-dipheny phosphine oxide 0.5 part, antioxidant 1010 0.2 part.
Wherein, polyhutadiene-polyether block acrylic resin II structural formula is as shown in the formula (in formula, m/n=2/3):
Above-mentioned various raw material is joined in clean planetary mixer successively according to described ratio, stirs 2h under 50 DEG C of conditions, after vacuumizing and defoaming, naturally leave standstill to room temperature, to obtain final product.
Embodiment 3
A kind of Liquid optical clear adhesive for module of entirely fitting; be made up of the material of the parts by weight described in following table: polyhutadiene-polyether block acrylic resin I 25 parts; urethane acrylate 25 parts, Hydroxyethyl acrylate 3 parts, tetrahydrofuran (THF) acrylate 19.2 parts; diethylene glycol dibenzoate 25 parts; 1-hydroxycyclohexyl phenyl ketone 6 parts, 2,4; 6-trimethylbenzoy-dipheny phosphine oxide 0.6 part, antioxidant 1010 0.5 part.
Described polyhutadiene-polyether block acrylic resin I structural formula is as shown in the formula (in formula m/n=1):
Above-mentioned various raw material is joined in clean planetary mixer successively according to described ratio, stirs 2h under 50 DEG C of conditions, after vacuumizing and defoaming, naturally leave standstill to room temperature, to obtain final product.
Embodiment 4
A kind of Liquid optical clear adhesive for module of entirely fitting; be made up of the material of the parts by weight described in following table: polyhutadiene-polyether block acrylic resin II 20 parts; urethane acrylate 25 parts, Hydroxyethyl acrylate 3 parts, tetrahydrofuran (THF) acrylate 24.2 parts; polyester polyol 25 parts; 1-hydroxycyclohexyl phenyl ketone 3.6 parts, 2,4; 6-trimethylbenzoy-dipheny phosphine oxide 0.9 part, antioxidant 1010 0.4 part.
Wherein, polyhutadiene-polyether block acrylic resin II structural formula is as shown in the formula formula (in formula, m/n=2/3):
Above-mentioned various raw material is joined in clean planetary mixer successively according to described ratio, stirs 2h under 50 DEG C of conditions, after vacuumizing and defoaming, naturally leave standstill to room temperature, to obtain final product.
Embodiment 5
A kind of Liquid optical clear adhesive for module of entirely fitting; be made up of the material of the parts by weight described in following table: polyhutadiene-polyether block acrylic resin I 20 parts; urethane acrylate 35 parts, Hydroxyethyl acrylate 4 parts, tetrahydrofuran (THF) acrylate 18.2 parts; polyester polyol 25 parts; 1-hydroxycyclohexyl phenyl ketone 4.1 parts, 2,4; 6-trimethylbenzoy-dipheny phosphine oxide 0.8 part, antioxidant 1010 0.7 part.
Described polyhutadiene-polyether block acrylic resin I structural formula is as shown in the formula (in formula m/n=1):
Above-mentioned various raw material is joined in clean planetary mixer successively according to described ratio, stirs 2h under 50 DEG C of conditions, after vacuumizing and defoaming, naturally leave standstill to room temperature, to obtain final product.
In embodiment 1-5 and the day industry, the performance comparison of mark post product is as shown in table 1 below, and as can be seen from Table 1, the viscosity of the embodiment of the present invention 1, cure shrinkage, hardness, transmittance, the indices such as yellowness index are all better than mark post product in day industry.
Table 1
Claims (10)
1. the Liquid optical clear adhesive for module of entirely fitting, it is characterized in that, be made up of the material of following parts by weight: polyhutadiene-polyether block acrylic resin or polyhutadiene-polyether block methacrylic resin 0 ~ 40 part, acrylic resin or methacrylic resin 0 ~ 30 part, vinylformic acid reactive thinner or methacrylic acid reactive thinner 0 ~ 25 part, inert plasticizer 0 ~ 30 part, light trigger 0 ~ 10 part, antioxidant 0 ~ 2 part.
2. a kind of Liquid optical clear adhesive for module of entirely fitting according to claim 1, it is characterized in that, the structural formula of described polyhutadiene-polyether block acrylic resin is as follows:
Wherein R represents 1, do not comprise the one in the part of isocyanate groups in hexamethylene-diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate molecular structure, R1 represents one in-H ,-CH3 or two kinds.
3. a kind of Liquid optical clear adhesive for module of entirely fitting according to claim 1, it is characterized in that, described acrylic resin or methacrylic resin are the mixture of the one or more than one in epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, epoxy methacrylates, urethane methacrylate, polyester methacrylate, methacrylates and modifier thereof.
4. a kind of Liquid optical clear adhesive for module of entirely fitting according to claim 3, is characterized in that, described acrylic resin polyether acrylate.
5. a kind of Liquid optical clear adhesive for module of entirely fitting according to claim 1, it is characterized in that, described vinylformic acid reactive thinner or methacrylic acid reactive thinner are one or more the mixture in isobornyl acrylate, isobornyl methacrylate, tetrahydrofuran (THF) acrylate, acrylic silicon ester, vinylformic acid Bian ester, lauric acid acrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, stearic acid acrylate, isodecyl acrylate.
6. a kind of Liquid optical clear adhesive for module of entirely fitting according to claim 1, it is characterized in that, described inert plasticizer is one or more mixtures in polyether glycol, polyester polyol, liquid polybutadiene resin, liquid polyisoprene resin, dipropylene glycol dibenzoate, diethylene glycol dibenzoate, di-alcohol diacrylate, dibutylene glycol diacrylate.
7. a kind of Liquid optical clear adhesive for module of entirely fitting according to claim 1; it is characterized in that; described light trigger is 2-hydroxy-methyl phenyl-propane-1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone, benzoin dimethylether, benzophenone, different monooctyl ester of contraposition N, N-dimethylaminobenzoic acid, 2; 4; 6-trimethylbenzoy-dipheny phosphine oxide, 2; one or more mixture in 4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester.
8. a kind of Liquid optical clear adhesive for module of entirely fitting according to claim 1, it is characterized in that, described oxidation inhibitor is Hinered phenols antioxidant.
9. a kind of Liquid optical clear adhesive for module of entirely fitting according to claim 1, it is characterized in that, described Hinered phenols antioxidant is antioxidant 1010.
10. for a preparation method for the Liquid optical clear adhesive of module of entirely fitting, it is characterized in that, raw material various described in claim 1 is joined in clean planetary mixer according to described ratio successively, 2h is stirred under 50 DEG C of conditions, after vacuumizing and defoaming, naturally leave standstill to room temperature, to obtain final product.
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Cited By (5)
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CN106120475A (en) * | 2016-06-27 | 2016-11-16 | 福建省优雅环保壁纸有限公司 | A kind of method using nano titanium oxide to produce the wallpaper with function of purifying indoor air |
CN106200065A (en) * | 2016-07-15 | 2016-12-07 | 武汉华星光电技术有限公司 | Mobile device and preparation method thereof |
EP3184568A1 (en) | 2015-12-21 | 2017-06-28 | Evonik Degussa GmbH | Acrylate-terminated urethane polybutadienes from low-monomer 1:1 monoadductes from reactive olefinic compounds and diisocyanates and hydroxy-terminated polybutadienes for liquid optically clear adhesives (locas) |
TWI634166B (en) * | 2016-05-17 | 2018-09-01 | 國立高雄大學 | Copolymer resin material and manufacturing method thereof |
EP4095164A1 (en) * | 2021-05-27 | 2022-11-30 | Evonik Operations GmbH | Universal adhesion promoters based on organofunctionally modified polybutadienes |
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WO2013039226A1 (en) * | 2011-09-14 | 2013-03-21 | 電気化学工業株式会社 | Composition and method for temporarily fixing member using same |
CN103031053A (en) * | 2013-01-06 | 2013-04-10 | 北京海斯迪克新材料有限公司 | UV-cured peelable blue gel for temporary protection of touch screen and preparation method thereof |
CN103160212A (en) * | 2011-12-19 | 2013-06-19 | 烟台德邦科技有限公司 | Ultraviolet light curing optical adhesive |
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Patent Citations (4)
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WO2013039226A1 (en) * | 2011-09-14 | 2013-03-21 | 電気化学工業株式会社 | Composition and method for temporarily fixing member using same |
CN102426494A (en) * | 2011-09-26 | 2012-04-25 | 上海佑威新材料科技有限公司 | Bonding method of touch screen substrates, and binder for same |
CN103160212A (en) * | 2011-12-19 | 2013-06-19 | 烟台德邦科技有限公司 | Ultraviolet light curing optical adhesive |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3184568A1 (en) | 2015-12-21 | 2017-06-28 | Evonik Degussa GmbH | Acrylate-terminated urethane polybutadienes from low-monomer 1:1 monoadductes from reactive olefinic compounds and diisocyanates and hydroxy-terminated polybutadienes for liquid optically clear adhesives (locas) |
US10385240B2 (en) | 2015-12-21 | 2019-08-20 | Evonik Degussa Gmbh | Acrylate-terminated urethane polybutadienes from low-monomer 1:1 monoadducts from reactive olefinic compounds and diisocyanates and hydroxy-terminated polybutadienes for liquid optically clear adhesives (LOCAs) |
TWI634166B (en) * | 2016-05-17 | 2018-09-01 | 國立高雄大學 | Copolymer resin material and manufacturing method thereof |
CN106120475A (en) * | 2016-06-27 | 2016-11-16 | 福建省优雅环保壁纸有限公司 | A kind of method using nano titanium oxide to produce the wallpaper with function of purifying indoor air |
CN106200065A (en) * | 2016-07-15 | 2016-12-07 | 武汉华星光电技术有限公司 | Mobile device and preparation method thereof |
EP4095164A1 (en) * | 2021-05-27 | 2022-11-30 | Evonik Operations GmbH | Universal adhesion promoters based on organofunctionally modified polybutadienes |
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