CN108329885B - Application of photosensitive resin composition as LED (light-emitting diode) curable OCA (optical clear adhesive) - Google Patents

Application of photosensitive resin composition as LED (light-emitting diode) curable OCA (optical clear adhesive) Download PDF

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CN108329885B
CN108329885B CN201710035630.6A CN201710035630A CN108329885B CN 108329885 B CN108329885 B CN 108329885B CN 201710035630 A CN201710035630 A CN 201710035630A CN 108329885 B CN108329885 B CN 108329885B
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led
cycloalkyl
resin composition
photosensitive resin
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CN108329885A (en
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钱晓春
胡春青
金晓蓓
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention discloses application of a photosensitive resin composition as an LED (light-emitting diode) curable OCA (optical clear adhesive), wherein the composition comprises an anthracene ester sensitizer, a photocurable oligomer, a monomer for viscosity adjustment and a photoinitiator. Through component adjustment, the epoxy resin adhesive film is suitable for free radical, cation or hybrid curing systems, has good LED curing property, low cost, good adhesive property when used as OCA, flexible and controllable adhesive layer thickness, and excellent transparency and yellowing resistance of the cured adhesive film.

Description

Application of photosensitive resin composition as LED (light-emitting diode) curable OCA (optical clear adhesive)
Technical Field
The invention belongs to the field of light-cured adhesives, and particularly relates to an application of a photosensitive resin composition as an LED-curable Optically Clear Adhesive (OCA).
Background
Optically Clear Adhesives (OCAs) are special adhesives for gluing transparent optical elements, and are one of the key raw materials in capacitive touch screen technology. As touch screens become more prevalent, the amount of OCA used has increased explosively. The curable adhesive for bonding the capacitive touch screen is mainly used for bonding a lens and a sensor in the touch screen and bonding a touch screen panel and a display, and has to meet certain requirements, such as: colorless and transparent, light transmittance of more than 90 percent, resistance to damp-heat aging, resistance to yellowing, no harm or low toxicity to human bodies and the like. Currently, the OCA technology is mainly held by several international companies such as 3M, Sony, japan chemical, and telecommunications, and forms a great barrier to patents.
The former OCA is a thermosetting product, has low production efficiency, andthe use of the adhesive on heat-sensitive substrates is limited, and the adhesive is gradually replaced by a UV curing adhesive which is green, environment-friendly and high in production efficiency in recent years. For example, the trade name 3MTM2175. The products of EAS-1616 and EAS-1614 are all UV-curable OCAs. Most of the photoinitiators used in the existing photocuring OCA are alpha-hydroxy ketone or benzil traditional initiators, and a radiation light source matched with the initiators is a high-pressure mercury lamp. As is well known, the use of mercury lamps as radiation sources is increasingly limited because of their low energy conversion rate, their preheating before operation, their high heat generation during operation, and their ozone generation which causes environmental pollution. The UV-LED has the advantages of small volume, high efficiency, long service life, low temperature, no ozone generation and the like, and is a preferential substitute for replacing a mercury lamp as a light source of the light-cured OCA. However, existing photocurable OCAs (e.g., compositions disclosed in documents CN104797672A, CN102153953A, etc.) are difficult to cure (no curing or extremely slow curing speed) under LED light sources, resulting from the fact that the absorption wavelength of the photoinitiator cannot be matched with the emission wavelength of the LED. Therefore, the development of the OCA which can be rapidly cured under the LED light source has very important significance and application value.
In addition, most of the existing photocurable OCAs are radical curing systems, and have large volume shrinkage during curing, which may cause severe stress effect, so that a cationic curing system or a radical-cationic hybrid curing system needs to be developed.
Disclosure of Invention
The invention aims to use an OCA composition capable of realizing LED rapid curing, which is a photosensitive resin composition, can be a free radical curing system, a cationic curing system or a free radical-cationic hybrid curing system through component adjustment, has good LED curing performance, low cost, good adhesive property when used as an OCA, flexible and controllable adhesive layer thickness, and excellent transparency and yellowing resistance of an adhesive film after curing.
Specifically, the invention relates to application of a photosensitive resin composition as an LED curable OCA, which is characterized by comprising the following components:
(A) the anthracene ester sensitizer is selected from a compound with a structure shown in a formula (I) and/or a macromolecular compound taking the compound shown in the formula (I) as a main structure:
Figure BDA0001211619510000031
wherein R is1-R10Each independently represents hydrogen, nitro, cyano, halogen, C1-C40Straight or branched alkyl of (2), C3-C40Cycloalkyl of, C4-C40Alkylcycloalkyl or cycloalkylalkyl, C2-C40Alkenyl of (C)6-C40Aryl of (C)4-C40Heteroaryl of (A), C2-C40A heterocyclyl group of-O-CO-R, and R1-R10At least one is an-O-CO-R group;
r represents C1-C40Straight or branched alkyl of (2), C3-C40Cycloalkyl of, C4-C40Alkylcycloalkyl or cycloalkylalkyl, C2-C40Alkenyl of (C)6-C40Aryl of (C)2-C40Containing an ester group, C2-C40An epoxy-containing group of (a);
and, non-cyclic-CH in these groups2-may be optionally substituted by-O-, -CO-, -NH-, -S-or 1, 4-phenylene;
(B) a photocurable oligomer;
(C) a monomer for viscosity adjustment;
(D) a photoinitiator.
Further, the invention provides an OCA optical adhesive tape, which sequentially comprises a light-stripping PET release film layer, an optical adhesive layer and a heavy-stripping PET release film layer from top to bottom, and is characterized in that: the optical adhesive layer is formed by the photosensitive resin composition.
Anthracenyl esters as component (A), in the definition of which, non-cyclic-CH2-means-CH not in a cyclic structure2-, i.e. excluding-CH in cyclic structures2-；“R1-R10"represents R1、R2、R3、R4、R5、R6、R7、R8、R9And R10。
Preferably, in the structure represented by the formula (I), R1-R10Each independently represents hydrogen, nitro, cyano, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C20Alkenyl of (C)6-C20Aryl of (C)4-C20Heteroaryl of (A), C2-C20A heterocyclyl group of-O-CO-R, and R1-R10At least one is an-O-CO-R group; r represents C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C20Alkenyl of (C)6-C20Aryl of (C)2-C20Containing an ester group, C2-C20An epoxy-containing group of (a); and, non-cyclic-CH in these groups2-may be optionally substituted by-O-, -CO-, -NH-, -S-or 1, 4-phenylene.
More preferably, in the structure of formula (I), R1-R10Each independently represents hydrogen, nitro, cyano, halogen, C1-C10Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C15Alkylcycloalkyl or cycloalkylalkyl, C2-C10Alkenyl of (C)6-C10Aryl of (C)4-C10Heteroaryl of (A), C2-C10A heterocyclyl group of-O-CO-R, and R1-R10At least one is an-O-CO-R group; r represents C1-C10Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C14Alkylcycloalkyl or cycloalkylalkyl, C2-C10Alkenyl of (C)6-C10OfBase, C3-C20Containing an ester group, C3-C20An epoxy-containing group of (a); and, non-cyclic-CH in these groups2-may be optionally substituted by-O-, -CO-, -NH-, -S-or 1, 4-phenylene.
In the optional groups of R, the ester group-containing group means that the group contains at least one-CO-O-or-O-CO-, and may be, for example, a group containing a (meth) acrylate group; preferably, the other moieties of the ester-containing group, besides the ester group, belong to the alkyl structure and/or the alkenyl structure. The epoxy-containing group means that the group contains at least one epoxy group (e.g., C)2-C3Epoxy groups); preferably, the other moieties of the epoxy-containing group, except the epoxy group, are of alkyl structure.
R of the formula (I)1-R10At least one of which is an-O-CO-R group. The number of-O-CO-R groups may be 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10, preferably 1, 2, 3 or 4. When more than two-O-CO-R groups are present in the structure of formula (I), R may be the same or different.
Further preferably, in the-O-CO-R group, R may be selected from the following groups:
C2-C8linear or branched alkyl of (a);
C2-C8alkenyl of (a);
Figure BDA0001211619510000051
wherein h is 0-3, i is 1-4, and the hydrogen on the cycloalkyl group is optionally substituted by C1-C4Alkyl substituted;
-(CH2)j-CO-O-CkH2k+1or- (CH)2)j-O-CO-CkH2k+1Wherein j is 0-4, k is 1-8;
-(CH2)r-O-CO-CH＝CH2wherein r is 0-5;
Figure BDA0001211619510000052
wherein m is 0-3 and n is 0-5;
Figure BDA0001211619510000053
wherein x is 0-3, y is 1-2, and z is 0-3;
Figure BDA0001211619510000054
wherein p is 0-5 and q is 0-5;
h. the hydrogen in the structure of j, r, m, x, y, p is optionally substituted by C1-C4Alkyl substituted; and acyclic-CH in these radicals2-is optionally substituted by-O-or-CO-. In the above groups, CkH2k+1、CnH2n+1、CzH2z+1And CqH2q+1Represents a linear or branched alkyl group having the corresponding number of carbon atoms; carbon number values include end values and integer values therebetween, e.g. h-0-3 means that h may be 0, 1, 2 or 3; these are well defined and obvious to those skilled in the art.
In the present invention, the compound having the structure represented by formula (I) can be obtained commercially or can be conveniently prepared by a conventionally known method. For example, reference may be made to the methods described in CN104991418A, CN105001081A, CN105037587A, the entire contents of which are hereby incorporated by reference.
As an optional anthracene ester sensitizer, the macromolecular compound with the compound of formula (I) as a main structure can be a macromolecular compound formed by polymerization (including homopolymerization and copolymerization), esterification or ester exchange reaction of the compound of formula (I). The corresponding synthesis methods can refer to the contents described in the Chinese patent applications with publication numbers CN104991418A and CN105001081A, which are incorporated herein by reference in their entireties.
Illustratively, the anthracene ester sensitizer as component (a) may be one or a combination of two or more of the compounds represented by the following structures:
Figure BDA0001211619510000061
Figure BDA0001211619510000071
Figure BDA0001211619510000081
Figure BDA0001211619510000091
Figure BDA0001211619510000101
Figure BDA0001211619510000111
Figure BDA0001211619510000121
Figure BDA0001211619510000131
in the photosensitive resin composition, the anthracene ester sensitizer as the component (a) may be a single compound or a combination of two or more compounds selected from a compound having a structure represented by formula (I) and/or a macromolecular compound having a compound of formula (I) as a main structure. The content of the anthracene ester sensitizer of the component (A) in the composition is 0.01-5%, preferably 0.01-3%, more preferably 0.1-2% by mass.
Component (B) is a photocurable oligomer, which may be a free radically polymerizable oligomer, a cationically polymerizable oligomer, or a combination of both.
The radical polymerizable oligomer may be any of those conventionally used in ultraviolet light curable OCAs, and examples thereof include epoxy acrylate oligomer, urethane acrylate oligomer, polyester acrylate oligomer, polyether acrylate oligomer, (meth) acrylate oligomer, and polybutadiene oligomer; urethane acrylate oligomers and polybutadiene oligomers are preferred.
Illustrative urethane acrylate oligomers which can be used in component (B) of the present invention include, but are not limited to: products (produced by Changxing company) with the trade names 6101-100, 611A-85, 6112-100, 6113, 6114, 6123, 6131, 6144-100, 6150-100, 6160B-70, 621A-80, 621-100, EX-06, 6315, 6320, 6323-100, 6325-100, 6327-100, 6336-100 or 6361-100; products (manufactured by sandoma corporation) having a commercial name of CN9001, CN9002, CN9004, CN9006, CN9014, CN9021, CN963J75, CN9002, CN966J75, CN973J75, CN962, CN964, CN965, CN940, CN945 or CN990, and the like. Polybutadiene oligomers which can be used in component (B) of the present invention are exemplified by, but not limited to: products with trade names CN301, CN302, CN303 (manufactured by sandomar); products with the trade names BR-641, BR-643 (manufactured by Bomar corporation); products (manufactured by Osaka organic chemical Co., Ltd.) having trade names BAC-45, BAC-15, PIPA, etc.
The cationically polymerizable oligomer can reduce the stress effect caused by volume shrinkage during curing of the OCA, and may be selected from the group consisting of alicyclic epoxy oligomers, hydrogenated epoxy oligomers, aromatic epoxy oligomers, aliphatic epoxy oligomers, and oxetane compounds.
Illustrative examples of the epoxy-based oligomer which can be used for the component (B) of the present invention include, but are not limited to: products under the trade names UVACURE 1500, UVACURE 1533, UVACURE 1534, UVACURE 1561, UVACURE 1562 (manufactured by cyanogen corporation); products (produced from new star materials) under the trade names 615, E-54, 0164, E-51, E-44, E-42, E-31, E-21, E-20. The oxetane compounds which can be used in the component (B) of the present invention are exemplified by, but not limited to: products having trade names of OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-213, OXT-610, OXMA (manufactured by east Asia synthetic Co., Ltd.); products sold under the trade names ETERNACOLL (R) EHO, ETERNACOLL (R) OXBP, ETERNACOLL (R) OXMA, ETERNACOLL (R) HBOX, ETERNACOLL (R) OXIPA (produced by Yu Ming Co., Ltd.); and those oxetanes disclosed in chinese patent application nos. 201610548580.7 and 201610550205.6, which are incorporated herein by reference in their entirety.
The photocurable oligomer of component (B) may be a mixture of one or more kinds of radical polymerizable oligomers, a mixture of one or more kinds of cationically polymerizable oligomers, or a mixture of two kinds of polymerizable oligomers.
The content of the component (B) in the photosensitive resin composition is 20 to 90% by mass, preferably 40 to 85% by mass, more preferably 50 to 80% by mass.
The viscosity-adjusting monomer as component (C) may be a monofunctional monomer, a polyfunctional monomer, or a mixture thereof, and may be selected from one or a combination of two or more of (meth) acrylic monomers, (meth) acrylic ester monomers, vinyl ether monomers, and epoxy monomers.
Illustrative, monomers that can be used for the component (C) of the present invention include, but are not limited to: monomer products (produced by changxing company) under the trade names EM223, EM328, EM2308, EM231, EM219, EM90, EM70, EM235, EM2381, EM2382, EM2384, EM2385, EM2386, EM2387, EM331, EM3380, EM241, EM2411, EM242, EM2421, EM 265; monomer products (manufactured by Saedoma) having trade names PM-1, PM-2, SR9008, SR9009, SR9011, SR9012, SR9016, CD550, CD551, CD552, and CD 553; monomer products having trade names of OXE-10 and OXE-30 (manufactured by Osaka, Japan); the single products (manufactured by titel corporation) under the trade names TTA21, TTA26, TTA11, TTA28, TTA15, TTA22, TTA27, TTA34, TTA500, TTA520, TTA182, TTA184, TTA186, and the like.
The content of the component (C) in the composition is 5 to 80% by mass, preferably 10 to 50% by mass, more preferably 20 to 40% by mass.
As the component (D), the kind of the photoinitiator should be adapted to the compositional classes of the reactive components, i.e., the components (B) and (C), to determine whether it is a radical type photoinitiator, a cationic type photoinitiator, or a combination of both. As is conventional knowledge to those skilled in the art.
Suitable free radical photoinitiators may be selected from one or more of benzoin, acetophenones, alpha-hydroxyketones, alpha-aminoketones, acylphosphine oxides, benzophenones, thioxanthones, anthraquinones, and oxime ester photoinitiators. Suitable cationic photoinitiators may be one or more of aryl diazonium salts, iodonium salts, sulfonium salts, aryl ferrocenium salts.
Illustrative examples of photoinitiators which can be used in component (D) of the present invention include, but are not limited to: products (manufactured by basf corporation) under the trade names Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 369, Irgacure 500, Irgacure 1000, Irgacure 819, Irgacure 1700, Irgacure 261, Irgacure 784, Irgacure 1173, Irgacure 2959, Irgacure 4265, Irgacure 4263; products (manufactured by sandomad) under the trade names SR1130, SR1137, SR1136, SR1135, SR1010, SR1011, SR1012, SR1125, and the like.
The content of the photoinitiator of component (D) in the photosensitive resin composition to be used is 0.1 to 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass.
In addition to the above components (a) to (D), it is obvious to those skilled in the art that organic or/and inorganic additives including, but not limited to, plasticizers, leveling agents, silane coupling agents, curing agents, antioxidants, stabilizers, etc. may be selectively added to the photosensitive resin composition according to application performance requirements. In addition, other sensitizers can be added into the composition for compounding use on the premise of not having negative influence on the application effect of the composition.
In the use according to the invention, the LEDs are preferably UV-LEDs emitting wavelengths between 200 and 450nm, in particular UV-LEDs having wavelengths such as those common at 365nm, 385nm, 395nm, 405nm and the like.
The photosensitive resin composition is used as an LED-curable OCA, and can be used for bonding or laminating various substrates, such as various parts in a display device, particularly for assembling light-transmitting parts, or bonding or laminating between light-transmitting substrates and between a light-transmitting substrate and a light-opaque substrate. The light-transmitting substrate may be glass or transparent plastic, etc.; the opaque substrate may be metal, opaque plastic, ceramic, stone, leather, wood, or the like. In use, the OCA exhibits good LED curability and adhesion, and the adhesive film is excellent in transparency and yellowing resistance.
Detailed Description
The present invention will be further specifically described with reference to the following examples, but it should not be construed as limiting the scope of the present invention.
1. Preparation of LED curable OCA
Referring to the formulations shown in examples 1-8 in Table 1, the raw materials were mixed uniformly. Parts are parts by mass unless otherwise indicated.
TABLE 1
Figure BDA0001211619510000171
Figure BDA0001211619510000181
The meaning of each component code in table 1 is shown below.
A-1：
Figure BDA0001211619510000182
A-2：
Figure BDA0001211619510000183
B-1: aliphatic urethane acrylate (6112-100, Changxin chemical engineering);
b-2: polybutadiene acrylate (CN301, sartomer chemical);
b-3: bisphenol a type epoxy resin (E-51, star new material);
B-4：
Figure BDA0001211619510000191
c-1: propylene glycol diacrylate (EM223, changxing chemical);
c-2: aliphatic epoxy resins (TTA21, titel);
d-1: 1-hydroxy-cyclohexyl-benzophenone (photoinitiator 184);
d-2: 4, 4' -dimethylphenyl hexafluorophosphate;
e-1: tert-butylhydroquinone.
For comparison, a photosensitive resin composition was prepared according to the formulation shown in comparative examples 1 to 4 in Table 2.
TABLE 2
Figure BDA0001211619510000192
Figure BDA0001211619510000201
2. Test of photocurability
The composition is stirred uniformly in a dark place, sampled on a glass substrate, coated by a wire rod, dried to obtain a coating with the thickness of 100 mu m, and then cured by respectively using a high-pressure mercury lamp and an LED as light sources. Wherein,
high-pressure mercury lamps: exposing in crawler-type exposure machine (model RW-UV20101), and receiving 2000mJ/cm cumulatively2Observing whether the film is solidified into a film or not;
LED: irradiating with UV-LED light source with wavelength of 395nm (Shenzhen blue spectrum Rick technology, Inc., model number LP300W 60-80V) at power of 1w/cm2Then, the film was exposed for 2 seconds to observe whether or not it was cured to form a film.
The results are shown in table 3.
TABLE 3
Figure BDA0001211619510000202
As can be seen from Table 3, the OCAs of the present invention cure rapidly in both LED and high pressure mercury lamp light sources, regardless of whether they are free radical, cationic or hybrid systems. The compositions of comparative examples 1 to 4 were good in photocurability under a high-pressure mercury lamp, but were not curable under an LED light source.
3. OCA Performance test
(1) Optical transmittance and yellowing
The composition was applied to a glass substrate and dried to form a coating layer having a thickness of 100. mu.m. 2000mJ/cm of OCA from examples 1 to 8 using UV-LED2Irradiation of comparative examples 1 to 4 was carried out using a high-pressure mercury lamp to accumulate 2000mJ/cm2And (4) irradiating to obtain a cured adhesive film.
The light transmittance after curing was measured using a haze meter (WGW photoelectric haze meter).
A total transmission scan was performed using a Color difference meter (Aicolor X-Rite Color i7, USA) with a scan wavelength of 400-700 nm. By Delta EabValue evaluation of yellowing,. DELTA.EabSmaller means less obvious yellowing, whereas more severe yellowing.
(2) Tackiness of the adhesive
The composition was coated to a thickness of 100 μm, and a glass slide having a thickness of 0.8mm and an acrylic resin plate having a thickness of 0.8mm were bonded to each other, and the thickness was 2000mJ/cm through glass using a UV-LED light source and a high-pressure mercury lamp, respectively2The sample is prepared by irradiation of (1).
The sample was left at 85 ℃ and 85% RH for 500 hours, and the presence or absence of flaking was visually observed.
O: no peeling;
x: there was peeling.
The evaluation results are shown in table 4.
TABLE 4
Figure BDA0001211619510000211
Figure BDA0001211619510000221
As can be seen from the detection results in Table 4, the photosensitive resin composition of the present invention has good LED curing performance when used as OCA, and the film transmittance exceeds 99%, Δ EabThe value is small, the yellowing resistance is good, a sample does not peel off in an adhesive property test, and the adhesive property is good. All the performances are basically consistent with the performances of the product after curing under the light source of a high-pressure mercury lamp.
The compositions of comparative examples 1-4 had similar performance under high pressure mercury lamps, but could not be cured under LED, and thus could not be used as LED cured OCA.

Claims (6)

1. Use of a photosensitive resin composition as an LED-curable OCA, characterized in that the photosensitive resin composition comprises the following components:
(A) the anthracene ester sensitizer is selected from a compound with a structure shown in a formula (I) and/or a macromolecular compound taking the compound shown in the formula (I) as a main structure:
Figure FDA0002969096120000011
wherein,
R1-R10each independently represents hydrogen, nitro, cyano, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C20Alkenyl of (C)6-C20Aryl of (C)4-C20Heteroaryl of (A), C2-C20A heterocyclyl group of-O-CO-R, and R1-R10At least one is an-O-CO-R group;
r represents C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkyl cycloalkyl or cycloalkyl ofAlkyl radical, C2-C20Alkenyl of (C)6-C20Aryl of (C)2-C20Containing an ester group, C2-C20An epoxy-containing group of (a);
and, non-cyclic-CH in these groups2-may be optionally substituted by-O-, -CO-, -NH-, -S-or 1, 4-phenylene;
(B) a cationically polymerizable oligomer selected from the group consisting of alicyclic epoxy oligomers, hydrogenated epoxy oligomers, aromatic epoxy oligomers, aliphatic epoxy oligomers, and oxetane compounds;
(C) a viscosity-adjusting monomer selected from epoxy monomers;
(D) a photoinitiator.
2. Use according to claim 1, characterized in that: in the structure of formula (I), R1-R10Each independently represents hydrogen, nitro, cyano, halogen, C1-C10Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C15Alkylcycloalkyl or cycloalkylalkyl, C2-C10Alkenyl of (C)6-C10Aryl of (C)4-C10Heteroaryl of (A), C2-C10A heterocyclyl group of-O-CO-R, and R1-R10At least one is an-O-CO-R group; r represents C1-C10Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C14Alkylcycloalkyl or cycloalkylalkyl, C2-C10Alkenyl of (C)6-C10Aryl of (C)3-C20Containing an ester group, C3-C20An epoxy-containing group of (a); and, non-cyclic-CH in these groups2-may be optionally substituted by-O-, -CO-, -NH-, -S-or 1, 4-phenylene.
3. Use according to claim 1 or 2, characterized in that: -O-CO-R, wherein R is selected from the group consisting of:
C2-C8linear or branched alkyl of (a);
C2-C8alkenyl of (a);
Figure FDA0002969096120000021
wherein h is 0-3, i is 1-4, and the hydrogen on the cycloalkyl group is optionally substituted by C1-C4Alkyl substituted;
-(CH2)j-CO-O-CkH2k+1or- (CH)2)j-O-CO-CkH2k+1Wherein j is 0-4, k is 1-8;
-(CH2)r-O-CO-CH＝CH2wherein r is 0-5;
Figure FDA0002969096120000022
wherein m is 0-3 and n is 0-5;
Figure FDA0002969096120000023
wherein x is 0-3, y is 1-2, and z is 0-3;
Figure FDA0002969096120000031
wherein p is 0-5 and q is 0-5;
h. the hydrogen in the structure of j, r, m, x, y, p is optionally substituted by C1-C4Alkyl substituted; and acyclic-CH in these radicals2-is optionally substituted by-O-or-CO-.
4. Use according to claim 1 or 2, characterized in that: the LED is a UV-LED emitting between 200 and 450 nm.
5. Use according to claim 3, characterized in that: the LED is a UV-LED emitting between 200 and 450 nm.
6. The utility model provides a OCA optical adhesive tape, from last to peeling off PET in proper order down from type rete, optical cement layer and heavy peeling off PET from type rete, its characterized in that: the optical adhesive layer is formed from the photosensitive resin composition as set forth in any one of claims 1 to 5.
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