CN110982346A - Ink composition, packaging structure and semiconductor device - Google Patents

Ink composition, packaging structure and semiconductor device Download PDF

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Publication number
CN110982346A
CN110982346A CN201911275797.5A CN201911275797A CN110982346A CN 110982346 A CN110982346 A CN 110982346A CN 201911275797 A CN201911275797 A CN 201911275797A CN 110982346 A CN110982346 A CN 110982346A
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unsubstituted
substituted
photocurable
group
ink composition
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洪海兵
王士昊
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Hangzhou First Applied Material Co Ltd
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Hangzhou First Applied Material 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds

Abstract

The invention provides an ink composition, a packaging structure and a semiconductor device. The ink composition comprises a photocurable silicon-containing monomer component, an active diluent component and a photoinitiator component, wherein the photocurable silicon-containing monomer component is a photocurable silicon-containing monomer or a combination of a plurality of photocurable silicon-containing monomers, and each photocurable silicon-containing monomer has a structural formula:
Figure DDA0002315518620000011
and A is1And A2At least one of which is an acrylate group, A1And A2At least one of which is an epoxy group. The monomer containing two functional groups of acrylate and epoxy is mixed for use to form a free radical-cation hybrid curing system, so that the material integrating the advantages of the acrylate and epoxy light-curable silicon-containing monomer is obtained, and the high light curing rate, the low curing shrinkage rate and the substrate adhesion are realizedAnd an organic barrier layer of moderate hardness. Thereby better satisfying the requirements of the prior art on the packaging film.

Description

Ink composition, packaging structure and semiconductor device
Technical Field
The invention relates to the technical field of packaging materials, in particular to an ink composition, a packaging structure and a semiconductor device.
Background
Organic Light-Emitting Diodes (OLEDs for short) have the characteristics of all solid-state, active Light emission, high brightness, high contrast, ultra-thin and ultra-Light, low cost, low power consumption, no view angle limitation, wide working temperature range and the like, can be manufactured on a flexible, Light and durable plastic substrate, can realize flexible display in the true sense, and is a technology which can best meet the requirements of people on future displays.
The currently applied various light emitting diodes mainly comprise organic small molecule light emitting diodes (OLEDs), Polymer Organic Light Emitting Diodes (POLED), organic phosphorescent light emitting diodes (PHOLEDs) and organic thermal excitation delay light emitting materials (TADFs). However, the biggest problem of the OLED is that the OLED has a shorter lifetime than the LCD, and the lifetime is only about 5000 hours, which is significantly inferior to the lifetime of the LCD. The service life of the OLED device is a key problem which besets many experts and scholars of the OLED at present, and is a bottleneck for restricting the development of the OLED industry. The factors influencing the service life of the OLED device are many, and physical factors such as the structure of the device, the circuit driving mode and the like exist; there are also chemical factors such as oxidation of the metal cathode, crystallization of the organic material, etc. Although the failure mechanism of OLEDs is not fully understood, there are many studies that suggest that the presence of moisture and oxygen inside the OLED device is a major factor in the lifetime of OLEDs. According to the research of the Kodak company on the OLED service life improving method, the research on the packaging technology is the most direct and obvious method in terms of solving the service life problem of the device.
For OLED devices, if the lifetime of the device is longer than 1 ten thousand hours, the Water Vapor Transmission Rate (WVTR) of the device needs to be less than 10 < -6 > g/m2(ii)/day, oxygen permeability (OTR) less than 10-5 g/(m)2D), which is a great challenge for the sealing structure of display devices, and therefore suitable OLED encapsulation technologies need to be developed.
The OLED packaging aims to isolate the light-emitting device from the environment, prevent the invasion of undesirable substances such as moisture, oxygen and the like, prevent external force damage, stabilize various parameters of the device and further prolong the service life of the OLED. The OLED packaging mainly comprises cover plate packaging, filler packaging, laser packaging, film packaging and the like.
In the traditional cover plate packaging, the prepared substrate and the cover plate are bonded together by using epoxy resin in a glove box filled with inert gas to form a closed space to isolate the device from the external environment, and components such as water, oxygen and the like in the air can only permeate into the device through the epoxy resin, so that the contact of the water and the oxygen in the air of each functional layer of the OLED is effectively prevented. The material of the package cover plate is generally glass or metal, but the light-tight property of the metal cover plate limits the application of the metal cover plate in device packaging. Although the glass cover plate package has no light transmission problem, the toughness is poor and the glass cover plate package is fragile.
The three packaging methods of laser packaging, filler packaging and film packaging do not need to use drying agents, and can be used in top-emitting OLED devices. The film packaging is to grow a single-layer or multi-layer film on the prepared OLED device substrate so as to achieve the effect of blocking water vapor. For the research of the OLED thin film, an organic-inorganic composite thin film method is generally used. The inorganic film can effectively block water vapor and oxygen, but has poor film forming property and interface matching property and is easy to form defects; the organic film has good flexibility, good film forming property and high flatness due to the large free volume and the large average degree of freedom of chain segments, and the defects of the inorganic film can be covered by the organic film. The inorganic film has high water vapor and oxygen barrier property and good surface morphology of the organic film, and the organic film and the inorganic film are alternately formed to be packaged to obtain satisfactory effect.
Thin film encapsulation is represented by a three-layer structure (PECVD-Flatness-PECVD), and the excellent performance of the thin film encapsulation is the mainstream way of flexible OLED encapsulation. The third laminated layer is obtained by using a first inorganic layer (SiNX) as a smooth substrate, printing an organic polymer buffer layer on the substrate by ink jet printing and then curing, and using a third inorganic layer (SiNX) as a last inorganic layer.
The existing packaging material systems are divided into two categories of epoxy and acrylate. The acrylate system generally has higher photocuring rate, but has extremely high requirement on the oxygen content in the curing environment, a small amount of oxygen can greatly reduce the curing rate, and meanwhile, the volume shrinkage is larger, and the adhesive force is poorer; the epoxy system is insensitive to oxygen content, has a slow curing speed, good adhesion and low curing shrinkage, needs high-temperature curing and has high hardness after curing, and is difficult to meet the increasingly developed flexible packaging requirements.
For example, Sanxing SDI corporation proposed an ink composition of silicone modified acrylates. The silicone-modified acrylate ink composition exhibits a higher photo-curing rate, a high light transmittance, and a low etching rate, compared to the acrylate ink composition without the silicone. However, it is difficult for the current ink compositions to satisfy the performance indexes such as high light curing rate and low curing shrinkage rate required for the increasing film packaging.
Compared with the common acrylate resin system packaging material, the epoxy resin system packaging material has lower curing shrinkage and better mechanical property. However, the conventional epoxy resin system encapsulation material generally requires thermal curing due to the slow curing speed, and the OLED suffers damage at high temperature, such as yellowing at high temperature, so that the conventional formulation must be modified to use UV curing.
Disclosure of Invention
The invention mainly aims to provide an ink composition, a packaging structure and a semiconductor device, and aims to solve the problem that a film packaging material in the prior art cannot give consideration to high light curing rate and low curing shrinkage rate.
In order to achieve the above objects, according to one aspect of the present invention, there is provided an ink composition comprising a photocurable silicon-containing monomer component, a reactive diluent component, and a photoinitiator component, the photocurable silicon-containing monomer component being a photocurable silicon-containing monomer or a combination of photocurable silicon-containing monomers, each photocurable silicon-containing monomer having the following structural formula I:
Figure BDA0002315518610000021
wherein n is any integer of 0 to 50; r1And R2Are the same or different and are each independently selected from: single bond, substituted or unsubstituted C1～C50Alkylene of (a), substituted or unsubstituted C3～C50Cycloalkylene group of (1), substituted or unsubstituted C1～C50Substituted or unsubstituted alkylene ether group ofC6～C50Arylene of (a), substituted or unsubstituted C7～C50Arylalkylene of (A), N- (R)3)-R4-、-O-R5-any of; wherein R is3Is hydrogen, substituted or unsubstituted C1～C50One of the alkyl groups of (1), R4Is substituted or unsubstituted C1～C50An alkylene group of (a); r5Is substituted or unsubstituted C1～C50An alkylene group of (a);
X1、X2、X3、X4are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C1～C50Alkyl, substituted or unsubstituted C1～C50Alkyl ether group of (A), substituted or unsubstituted C1～C50Cycloalkyl, substituted or unsubstituted C1～C50Alkyl sulfide group of (a), substituted or unsubstituted C6～C50Aryl, substituted or unsubstituted C3～C50Heteroaryl, substituted or unsubstituted C7～C50Aralkyl, -NR6R7Any one of the above; wherein R is6And R7Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C1～C50Any one of the alkyl groups of (a);
A1and A2Are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C1～C50Alkyl, substituted or unsubstituted C1～C60Alkyl ether group of (A), substituted or unsubstituted C1～C50Alkyl sulfide group of (a), substituted or unsubstituted C6～C50Aryl, substituted or unsubstituted C7～C50Aralkyl, -NR8R9Any one of a substituted or unsubstituted acrylate group; wherein R is8And R9Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C1～C50Any one of the alkyl groups of (a); and in photocurable silicon-containing monomer component，A1And A2At least one of them is represented by any one of structural formula II to structural formula IV, A1And A2At least one of which is represented by structural formula V:
Figure BDA0002315518610000031
wherein, denotes the binding site, Z1、Z2、Z3、Z4、Z5、Z6、Z7And Z8Each independently selected from hydrogen, substituted or unsubstituted C1～C50Any one of the alkyl groups of (1).
Further, n is an integer of 0 to 10, preferably R1And R2Each independently selected from: substituted or unsubstituted C1To C10Alkylene of, -O-R5Any one of-and-O-R5in-R5Is substituted or unsubstituted C1To C10One of alkylene groups of (1), preferably X1、X2、X3、X4Same or different, each independently selected from hydrogen, substituted or unsubstituted C1To C10Alkyl, substituted or unsubstituted C6To C10Aryl, substituted or unsubstituted C7To C11Any one of the aralkyl groups of (1), and X1、X2、X3、X4Is substituted or unsubstituted C6To C10Aryl, substituted or unsubstituted C7To C11Any one of the aralkyl groups of (1).
Further, the above-mentioned photocurable silicon-containing monomer component is a combination of several photocurable silicon-containing monomers, in which A of one photocurable silicon-containing monomer is1And A2Is a group represented by the formula III, preferably Z4、Z5、Z6Each independently selected from hydrogen, substituted or unsubstituted C1To C10More preferably, the alkyl group of (a) is hydrogen.
Further, onThe photo-curable silicon-containing monomer component is a combination of a plurality of photo-curable silicon-containing monomers, wherein A of one photo-curable silicon-containing monomer1And A2Is a group represented by the formula V, preferably Z8Selected from hydrogen, substituted or unsubstituted C1To C10More preferably, the alkyl group of (1) is a methyl group.
Further, A of at least one photocurable silicon-containing monomer of the above photocurable silicon-containing monomer components1Is a group represented by the formula V, and A2Is a group represented by structural formula III; preferably Z8Selected from hydrogen, substituted or unsubstituted C1To C10Any of the alkyl groups of (a), more preferably methyl; preferably Z4、Z5、Z6Each independently selected from hydrogen, substituted or unsubstituted C1To C10More preferably, the alkyl group of (a) is hydrogen.
Further, the reactive diluent component is any one or more of photocurable diluent monomers having one or more functional groups of 1 to 4 epoxy groups or oxetanyl groups and (meth) acryloyloxy groups, preferably the reactive diluent monomer has a structure represented by formula VI:
Figure BDA0002315518610000041
wherein Y is selected from: single bond, substituted or unsubstituted C1To C50Alkylene of (a), substituted or unsubstituted C3To C50Cycloalkylene group of (1), substituted or unsubstituted C1To C50Alkylene ether group of (A), substituted or unsubstituted C6To C50Arylene of (a), substituted or unsubstituted C7To C50Arylalkylene of-O-R10-、-N(R11)-R12-any of; wherein R is10Selected from substituted or unsubstituted C1To C50Any one of alkylene groups; r11Is hydrogen, substituted or unsubstituted C1To C50Any one of alkyl, R12Is a substitutionOr unsubstituted C1To C50Any one of alkylene groups; z9、Z10Each independently selected from hydrogen, substituted or unsubstituted C1～C50Alkyl, substituted or unsubstituted C1～C60And Z is any one of an alkyl ether group, a substituted or unsubstituted acrylate group9、Z10Is represented by any one of formula II, formula III, formula IV, formula V; more preferably, the reactive diluent component comprises at least two photocurable diluent monomers, and the two photocurable diluent monomers are each independently of the other a structure of formula VI, and wherein Z of one of the photocurable diluent monomers is9And Z10Each independently being a (meth) acryloyloxy group, Z being another photocurable diluent monomer9And Z10Each independently is one of 1 to 4 epoxy groups or oxetane groups.
Further, the above Y is selected from substituted or unsubstituted C1To C10Alkylene, substituted or unsubstituted C1To C10Alkylene ether group, substituted or unsubstituted C6To C10Arylene, substituted or unsubstituted C7To C11Any one of arylalkylene groups.
Further, the photoinitiator component includes a radical photoinitiator and a cationic photoinitiator, preferably, the radical photoinitiator is one or more of a benzoin-based radical photoinitiator, a benzil-based radical photoinitiator, an alkylbenzene-based radical photoinitiator, an acyl phosphorus oxide-based radical photoinitiator, a benzophenone-based radical photoinitiator, and a thioxanthone-based radical photoinitiator, and preferably, the cationic photoinitiator is one or more of a diaryliodonium salt cationic photoinitiator, a triarylsulfonium salt cationic photoinitiator, a diazonium salt cationic photoinitiator, an alkyl sulfonium salt cationic photoinitiator, an iron arene salt cationic photoinitiator, a sulfonyloxy ketone cationic photoinitiator, and a triarylsiloxane cationic photoinitiator.
Further, the ink composition comprises, by weight, 5-90% of a photocurable silicon-containing monomer component, 5-90% of a reactive diluent component, and 0.02-20% of a photoinitiator component, wherein a cationic photoinitiator and a free radical photoinitiator in the photoinitiator component are 0.01-10% respectively; preferably, the content of the photo-curable silicon-containing monomer component is 20-50%, the content of the reactive diluent component is 40-80%, and the content of the cationic photoinitiator and the content of the free radical photoinitiator are respectively and independently 1-8%.
Further, the ink composition further comprises an auxiliary component, preferably the auxiliary component is selected from any one or more of a polymerization inhibitor, a surfactant, an antioxidant, a defoaming agent and a leveling agent, and preferably the content of the auxiliary component is 0.01-5 wt%.
Further, the viscosity of the ink composition at 25 ℃ is 1 to 50 mPas.
According to another aspect of the present invention, there is provided an encapsulation structure comprising an organic layer formed by photocuring using any one of the ink compositions described above.
According to another aspect of the present invention, there is provided a semiconductor device comprising a functional structure and an encapsulation structure, wherein the encapsulation structure is the aforementioned encapsulation structure, and preferably the semiconductor device is any one of an electroluminescent device, a photoluminescent device, a lighting device, a light emitting diode, a solar cell, a thin film transistor and a photodetector.
By applying the technical scheme of the invention, the curable silicon-containing monomer with the structural formula I is adopted as a polymerized monomer, and in the photocurable silicon-containing monomer component, A1And A2At least one of which is represented by any one of structural formulas II to IV, A1And A2At least one of which is represented by structure V. That is, the present application combines monomers containing both acrylate and epoxy functionalities to form a free radical-cationic hybrid cure system when combined with a reactive diluent component. In the hybrid photocuring system, the free radical monomer can improve the photocuring rate of the system, increase the curing shrinkage rate of the system and reduce the adhesion of the system to a base materialForce application; and the cationic monomer can reduce the curing shrinkage of the system and improve the adhesion to the base material. The two are combined to obtain a material which integrates the advantages of the acrylic ester and the epoxy light-curable silicon-containing monomer, and the organic barrier layer with higher light curing rate, lower curing shrinkage rate and moderate base material adhesion and hardness is realized. Thereby better satisfying the requirements of the prior art for ink-jet printing.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art, the problem that the thin film encapsulation material cannot achieve both high light curing rate and low curing shrinkage rate exists in the prior art, and in order to solve the problem, the invention provides an ink composition, an encapsulation structure and a semiconductor device.
In one exemplary embodiment of the present application, an ink composition is provided that includes a photocurable silicon-containing monomer component, a reactive diluent component, and a photoinitiator component, the photocurable silicon-containing monomer component being a photocurable silicon-containing monomer or a combination of photocurable silicon-containing monomers, each photocurable silicon-containing monomer having the following structural formula I:
Figure BDA0002315518610000061
wherein n is any integer of 0 to 50; r1And R2Are the same or different and are each independently selected from: single bond, substituted or unsubstituted C1～C50Alkylene of (a), substituted or unsubstituted C3～C50Cycloalkylene group of (1), substituted or unsubstituted C1～C50Alkylene ether group of (A), substituted or unsubstituted C6～C50Arylene of (a), substituted or unsubstituted C7～C50Arylalkylene of (A), N- (R)3)-R4-、-O-R5-any of; wherein R is3Is hydrogen,Substituted or unsubstituted C1～C50One of the alkyl groups of (1), R4Is substituted or unsubstituted C1～C50An alkylene group of (a); r5Is substituted or unsubstituted C1～C50An alkylene group of (a);
X1、X2、X3、X4are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C1～C50Alkyl, substituted or unsubstituted C1～C50Alkyl ether group of (A), substituted or unsubstituted C1～C50Cycloalkyl, substituted or unsubstituted C1～C50Alkyl sulfide group of (a), substituted or unsubstituted C6～C50Aryl, substituted or unsubstituted C3～C50Heteroaryl, substituted or unsubstituted C7～C50Aralkyl, -NR6R7Any one of the above; wherein R is6And R7Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C1～C50Any one of the alkyl groups of (a);
A1and A2Are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C1～C50Alkyl, substituted or unsubstituted C1～C60Alkyl ether group of (A), substituted or unsubstituted C1～C50Alkyl sulfide group of (a), substituted or unsubstituted C6～C50Aryl, substituted or unsubstituted C7～C50Aralkyl, -NR8R9Any one of a substituted or unsubstituted acrylate group; wherein R is8And R9Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C1～C50Any one of the alkyl groups of (a); and in the photocurable silicon-containing monomer component, A1And A2At least one of them is represented by any one of structural formula II to structural formula IV, A1And A2At least one of which is represented by structural formula V:
Figure BDA0002315518610000062
wherein, denotes the binding site, Z1、Z2、Z3、Z4、Z5、Z6、Z7And Z8Each independently selected from hydrogen, substituted or unsubstituted C1～C50Any one of the alkyl groups of (1).
Because the photocurable silicon-containing monomer component is a photocurable silicon-containing monomer or a combination of a plurality of photocurable silicon-containing monomers, the curable silicon-containing monomer with the structural formula I is used as a polymerized monomer, and in the photocurable silicon-containing monomer component, A1And A2At least one of them is represented by any one of structural formula II to structural formula IV, A1And A2At least one of which is represented by structure V. That is, the present application combines the use of monomers containing both acrylate and epoxy functionalities to form a free radical-cationic hybrid cure system when combined with a reactive diluent component. In the hybrid photocuring system, the free radical monomer can improve the photocuring rate of the system, increase the curing shrinkage rate of the system and reduce the adhesive force of the system to a base material; and the cationic monomer can reduce the curing shrinkage of the system and improve the adhesion to the base material. The two are combined to obtain a material which integrates the advantages of the acrylic ester and the epoxy light-curable silicon-containing monomer, and the organic barrier layer with higher light curing rate, lower curing shrinkage rate and moderate substrate adhesion and hardness is realized. Thereby better satisfying the requirements of the prior art for ink-jet printing.
In order to further improve the photocurability and reduce the curing shrinkage, n is preferably an integer of 0 to 10, and R is preferably R1And R2Each independently selected from: substituted or unsubstituted C1To C10Alkylene of, -O-R5Any one of-and-O-R5in-R5Is substituted or unsubstituted C1To C10One of alkylene groups of (1), preferably X1、X2、X3、X4Same or different, each independently selected from hydrogen, substituted or unsubstituted C1To C10Alkyl, substituted or unsubstituted C6To C10Aryl, substituted or unsubstituted C7To C11Any one of the aralkyl groups of (1), and X1、X2、X3、X4Is substituted or unsubstituted C6To C10Aryl, substituted or unsubstituted C7To C11Any one of the aralkyl groups of (1).
In order to further promote the exertion of the performances of the epoxy light-curable silicon-containing monomer in the aspects of reducing the curing shrinkage rate of a system and improving the adhesion force to a substrate and obtain a better ink composition, the light-curable silicon-containing monomer component is a combination of a plurality of light-curable silicon-containing monomers, wherein A of one light-curable silicon-containing monomer is1And A2Is a group represented by the formula III, preferably Z4、 Z5、Z6Each independently selected from hydrogen, substituted or unsubstituted C1To C10More preferably, the alkyl group of (a) is hydrogen.
In order to further promote the exertion of the performances of the acrylate photocurable silicon-containing monomer in the aspects of improving the curing shrinkage rate of a system and improving the photocuring rate and obtain a better ink composition, the photocurable silicon-containing monomer component is a combination of a plurality of photocurable silicon-containing monomers, wherein A of one photocurable silicon-containing monomer is1And A2Is a group represented by the formula V, preferably Z8Selected from hydrogen, substituted or unsubstituted C1To C10More preferably, the alkyl group of (1) is a methyl group.
The performance of the ink composition is good and bad as a result of the combination of the epoxy group and the acrylate group in the photocurable silicon-containing monomer component. In order to obtain an ink composition with better performance by better matching of the two components, A of at least one photocurable silicon-containing monomer of the photocurable silicon-containing monomer component1Is a group represented by the formula V, and A2Is represented by structural formula IIIA group of (a); preferably Z8Selected from hydrogen, substituted or unsubstituted C1To C10Any of the alkyl groups of (a), more preferably methyl; preferably Z4、 Z5、Z6Each independently selected from hydrogen, substituted or unsubstituted C1To C10More preferably, the alkyl group of (a) is hydrogen.
In order to make the reactive diluent component more fully dilute the photocurable silicon-containing monomer component, so as to fully exert the performance of each monomer in the photocurable silicon-containing monomer component, thereby obtaining an ink composition with better performance, the reactive diluent component is any one or more of photocurable diluent monomers with one or more functional groups of 1 to 4 epoxy groups or oxetanyl groups and (methyl) acryloyloxy groups, preferably the reactive diluent monomer has a structure shown in a structural formula VI:
Figure BDA0002315518610000071
wherein Y is selected from: single bond, substituted or unsubstituted C1To C50Alkylene of (a), substituted or unsubstituted C3To C50Cycloalkylene group of (1), substituted or unsubstituted C1To C50Alkylene ether group of (A), substituted or unsubstituted C6To C50Arylene of (a), substituted or unsubstituted C7To C50Arylalkylene of-O-R10-、-N(R11)-R12-any of; wherein R is10Selected from substituted or unsubstituted C1To C50Any one of alkylene groups; r11Is hydrogen, substituted or unsubstituted C1To C50Any one of alkyl, R12Is substituted or unsubstituted C1To C50Any one of alkylene groups; z9、Z10Each independently selected from hydrogen, substituted or unsubstituted C1～C50Alkyl, substituted or unsubstituted C1～C60And Z is any one of an alkyl ether group, a substituted or unsubstituted acrylate group9、Z10Is represented by any one of formula II, formula III, formula IV, formula V; more preferably, the reactive diluent component comprises at least two photocurable diluent monomers, and the two photocurable diluent monomers are each independently of the other a structure of formula VI, and wherein Z of one of the photocurable diluent monomers is9And Z10Each independently being a (meth) acryloyloxy group, Z being another photocurable diluent monomer9And Z10Each independently is one of 1 to 4 epoxy groups or oxetane groups.
To further enhance the dilution of the reactive diluent and the complexing with the photocurable silicon-containing monomer component, Y is selected from the group consisting of substituted and unsubstituted C1To C10Alkylene, substituted or unsubstituted C1To C10Alkylene ether radical, substituted or unsubstituted C6To C10Arylene, substituted or unsubstituted C7To C11Any one of arylalkylene groups.
In order to more efficiently combine the monomer and the diluent to improve the polymerization efficiency of the photocurable silicon-containing monomer and achieve both the photocuring rate and the curing shrinkage of the ink composition, the photoinitiator component includes a radical photoinitiator and a cationic photoinitiator, preferably the radical photoinitiator is one or more of a benzoin radical photoinitiator, a benzil radical photoinitiator, an alkylbenzene free radical photoinitiator, an acyl phosphorus oxide free radical photoinitiator, a benzophenone free radical photoinitiator and a thioxanthone free radical photoinitiator, and preferably the cationic photoinitiator is a diaryliodonium salt cationic photoinitiator, a triarylsulfonium salt cationic photoinitiator, a diazonium salt cationic photoinitiator, an alkyl sulfonium salt cationic photoinitiator, an iron arene salt cationic photoinitiator, One or more of a sulfonyloxy ketone cationic photoinitiator and a triaryl siloxane cationic photoinitiator.
The curable silicon-containing monomer component, reactive diluent component, and photoinitiator component described above may be used in amounts conventionally used in the art for each type of material. In one embodiment of the present application, in order to improve the polymerization effect of the photocurable silicon-containing monomer and enable better matching of the epoxy photocurable silicon-containing monomer and the acrylate photocurable silicon-containing monomer, an ink composition with better overall performance is obtained. The ink composition comprises, by weight, 5-90% of a photocurable silicon-containing monomer component, 5-90% of a reactive diluent component, and 0.02-20% of a photoinitiator component, wherein a cationic photoinitiator and a free radical photoinitiator in the photoinitiator component are each independently 0.01-10%; preferably, the content of the photo-curable silicon-containing monomer component is 20-50%, the content of the reactive diluent component is 40-80%, and the content of the cationic photoinitiator and the content of the free radical photoinitiator are respectively and independently 1-8%.
In order to further improve the film forming performance of the ink composition, the ink composition further comprises an auxiliary component, preferably the auxiliary component is selected from any one or more of a polymerization inhibitor, a surfactant, an antioxidant, a defoaming agent and a leveling agent, and preferably the content of the auxiliary component is 0.01-5 wt%. The above-mentioned additives can be selected from the corresponding additives commonly used in the packaging film in the prior art, and are not listed here.
Each of the above components can be obtained from commercially available products or prepared by typical methods. The components are uniformly mixed at 25-40 ℃ for use.
The proper viscosity environment is beneficial to the polymerization of the photo-curable silicon-containing monomer in the ink composition, and the viscosity of the ink composition at 25 ℃ is 1-50 mPa & s to obtain the ink composition with excellent performance so as to meet the requirement of ink jet printing.
In another exemplary embodiment of the present application, there is provided an encapsulation structure including an organic layer formed by photocuring using any one of the above-described ink compositions.
The polymer film formed by the ink composition has higher photocuring rate and lower curing shrinkage, so that the optical requirement and curing speed requirement of a packaging structure are met, the polymer film has more proper viscosity, bonding strength, adhesive force and flexibility, and the packaging requirement of the mainstream inkjet printing mode at present is better met, and a better packaging effect is maintained.
The above-mentioned packaging structure may further include other functional material layers for achieving better packaging effect, and the present invention is not limited to this, and those skilled in the art can choose according to common knowledge or common technical means, for example, add an inorganic insulating material layer, i.e. a layer structure of a packaging layer formed by an inorganic insulating material, including but not limited to inorganic insulating materials such as metal oxide, metal nitride or metal sulfide. The inorganic insulating material may be formed into the inorganic insulating material layer by a variety of means including, but not limited to, vacuum evaporation, dc sputtering, ion beam deposition, and the like.
The photocurable encapsulating composition described above herein is disposed on a surface of a semiconductor device to be encapsulated and cured using UV radiation to form an encapsulating structure. Methods of disposing the photocurable encapsulating composition include, but are not limited to, ink jet printing.
In yet another exemplary embodiment of the present application, a semiconductor device is provided, which includes a functional structure and an encapsulation structure, the encapsulation structure is the above-mentioned encapsulation structure, and preferably, the semiconductor device is any one of an electroluminescent device, a photoluminescent device, a lighting device, a light emitting diode, a solar cell, a thin film transistor, and a photodetector.
The functional structure may be a member that may cause quality degradation or deterioration due to gas or liquid permeation in the environment, including but not limited to: electroluminescent devices, photoluminescent devices, lighting devices, light emitting diodes, solar cells, thin film transistors, and photodetectors.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. It should be understood that these examples are provided for illustration only and are not to be construed as limiting the invention in any way. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The following are examples of the preparation of each A (silicon-containing monomer):
example 1
In a 1000mL flask equipped with a cooling tube and a stirrer, 500mL of toluene, 54.11g of 1,1,3,5, 5-pentamethyl-3-phenyltrisiloxane and 74.51g of 4-vinyl-1-cyclohexene-1, 2-epoxy were placed, followed by nitrogen purge for 60 min. After this, 0.0063g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane was placed in a flask, the temperature of the flask was increased to 40 ℃, followed by stirring for 4 h. The residual solvent was removed by distillation, thereby preparing a compound represented by formula 1, which is denoted as I. The HPLC assay had a purity of 97%. 588.24 parts of m/e;1H NMR(400MHz,Chloroform-d)δ7.51(m,1H), δ7.28(m,2H),δ7.18(m,2H),δ1.45(m,4H),δ1.60(dd,2H),δ2.87(dd,2H),δ1.60-1.70(dd,4H), δ1.43(m,2H),δ1.3(m,4H),δ0.21(m,12H),δ0.66(s,3H),δ0.8(m,4H)。
[ formula 1]
Figure BDA0002315518610000101
Example 2
In a 1000mL flask equipped with a cooling tube and a stirrer, 800mL of toluene, 33.26g of 1,1,5, 5-tetramethyl-3, 3-diphenyltrisiloxane and 91.3g of allyl glycidyl ether were placed, followed by nitrogen purging for 60 min. After that, 0.0063g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane was put into a flask, and the temperature of the flask was increased to 70 ℃, followed by stirring for 4 h. The residual solvent was removed by distillation. A compound represented by formula 2, noted II, was thus prepared. Purity 97% by HPLC, m/e: 560.24;1H NMR(400MHz,Chloroform-d)δ7.53(m,2H),δ7.29(m,4H), δ7.19(m,4H),δ3.63(d,4H),δ3.38(m,4H),δ2.86(dd,2H),δ2.38(dd,4H),δ1.5(m,4H),δ1.02(m,4H), δ0.21(s,12H)。
[ formula 2]
Figure BDA0002315518610000102
Example 3
In a 1000mL flask equipped with a cooling tube and a stirrer, 800mL of toluene, 30g of 1,1,5, 5-tetramethyl-3-diphenyltrisiloxane and 50g of allyl alcohol were placed, followed by nitrogen purging for 60 min. After that, 0.003g of platinum (0) -1, 3-diethylene-1, 1,3, 3-tetramethyldisiloxane was put into a flask, and the temperature of the flask was increased to 70 ℃ followed by stirring 4 g. The residual solvent was removed by distillation to give a crude intermediate having a terminal hydroxyl group. The crude product was subjected to column chromatography of ethyl acetate and petroleum ether to give an intermediate product of 98% liquid chromatography purity, which was added to a three-necked flask containing 300mL of anhydrous dichloromethane, 21g of triethylamine was added, followed by slowly introducing 45g of acryloyl chloride while stirring at 0 ℃. The residual solvent was removed by distillation, thereby producing an intermediate product containing methylpropionyl. The above intermediate product was charged into a 500mL three-necked flask containing toluene, 36g of 4-vinyl-1-cyclohexene-1, 2-epoxy was added, followed by nitrogen purging for 60 min. After this, 0.003g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane was put into a flask, and the temperature of the flask was increased to 40 ℃ followed by stirring for 4 hours. The residual solvent was removed by distillation, whereby a compound represented by formula 3 was produced as III. Purity 97% by HPLC, m/e: 2590;1H NMR(400MHz，Chloroform-d)δ7.51(m,1H), δ7.28(m,2H),δ7.18(m,2H),δ6.58(d,1H),δ6.40(d,1H),δ2.01(s,3H),δ4.20(m,2H),δ1.60(dd,2H), δ2.87(dd,2H),δ1.60-1.70(dd,4H),δ1.43(m,1H),δ1.45(m,2H),δ0.21(m,12H),δ0.66(s,3H)。
[ formula 3]
Figure BDA0002315518610000111
Example 4
In a 1000mL flask equipped with a cooling tube and a stirrer, 800mL of toluene, 33.26g of 1,1,5, 5-tetramethyl-3, 3-diphenyltrisiloxane and 61.87g of [ [2- (allyloxy) phenoxy ] was placedBase of]Methyl radical]Ethylene oxide followed by a nitrogen purge for 60 min. After this, 0.0063g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane was placed in a flask, the temperature of the flask was increased to 70 ℃, followed by stirring for 4 h. The residual solvent was removed by distillation. A compound represented by formula 4, noted IV, was thus prepared. Purity 97% by HPLC, m/e: 748.13;1H NMR(400MHz,Chloroform-d)δ7.53-7.55(m,3H), δ7.29-7.31(m,6H),δ7.19-7.20(m,3H),δ3.63(d,4H),δ3.38(m,4H),δ2.86(dd,2H),δ2.38(dd,4H), δ1.5(m,4H),δ1.02(m,4H),δ0.21(s,12H)。
[ formula 4]
Figure BDA0002315518610000112
Example 5
In a 1000mL flask equipped with a cooling tube and a stirrer, 800mL of toluene, 54.11g of 1,1,3,5, 5-pentamethyl-3-phenyltrisiloxane and 80g of allyl alcohol were placed, followed by nitrogen purging for 60 min. After that, 0.0063g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane was put into a flask, and the temperature of the flask was increased to 70 ℃, followed by stirring for 5 hours. The residual solvent was removed by distillation. After 71.2g of the resultant compound was introduced into 400mL of methylene chloride, 39.64 g of triethylamine was added thereto, followed by slowly introducing 90g of acryloyl chloride while stirring at 0 ℃. The residual solvent was removed by distillation, thereby preparing a compound represented by formula 5, which is designated as V. Purity 97% by HPLC, m/e: 494.8;1HNMR(400 MHz，Chloroform-d)δ7.51(m,1H),δ7.28(m,2H),δ7.18(m,2H),δ6.27(d,2H),δ6.05(d,2H), δ5.95(d,2H),δ2.01(s,3H),δ4.20(m,4H),δ1.60(dd,4H),δ0.21(m,12H),δ0.66(d,4H)。
[ formula 5]
Figure BDA0002315518610000121
Example 6
In a 1000mL flask equipped with a cooling tube and a stirrer, 300mL of toluene, 33.26g of 1,1,5, 5-tetramethyl-3, 3-diphenyltrisiliconSiloxane and 30.33g of N-methylolacrylamide followed by a nitrogen purge for 30 min. After that, 0.0063g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane was put into a flask, and the temperature of the flask was increased to 40 ℃, followed by stirring for 4 hours. After the residual solvent was removed by distillation and the resulting product was introduced into 400mL of methylene chloride, 38.64g of triethylamine was added thereto, followed by slow introduction of 39.84g of methacryloyl chloride while stirring at 0 ℃. The residual solvent was removed by distillation, thereby preparing the compound represented by formula 6, noted VI. Purity 97% by HPLC, m/e: 670.26;1H NMR(400MHz，Chloroform-d)δ8.03(m,2H),δ7.52(m,2H),δ7.29(m,4H),δ7.19-7.20(m,4H), δ6.58(d,2H),δ6.40(d,2H),δ6.06(dd,4H),δ2.2(m,4H),δ2.01(s,6H),δ1.3(m,4H),δ0.21(s,12H)。
[ formula 6]
Figure BDA0002315518610000122
Example 7
In a 1000mL flask having a cooling tube and a stirrer, 800mL of toluene, 54g of 1,1,3,5, 5-pentamethyl-3, 3-diphenyltrisiloxane (n ═ 12) oligomer (TCI), and 10g of allyl alcohol were placed, followed by nitrogen purging for 60 min. After that, 0.002g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane was put into a flask, and the temperature of the flask was increased to 70 ℃, followed by stirring for 5 hours. The residual solvent was removed by distillation. After 8g of the resulting compound was introduced into 400mL of methylene chloride, 5g of triethylamine was added thereto, followed by slowly introducing 10g of acryloyl chloride while stirring at 0 ℃. The residual solvent was removed by distillation, thereby preparing a compound represented by formula 7, designated as VII. Purity 97% by HPLC, m/e: 2590;1H NMR(400MHz，Chloroform-d)δ7.52(m,24H),δ7.29(m,48H),δ7.19-7.20(m,48H),δ6.58(d,2H), δ6.06(dd,4H),δ3.6(m,4H),δ2.01(s,6H),δ1.3(m,4H),δ0.6(m,4H),δ0.21(s,12H)。
[ formula 7]
Figure BDA0002315518610000131
Example 8
In a 1000mL flask equipped with a cooling tube and a stirrer, 800mL of toluene, 67g of (dimethylamino) (phenyl) silyldimethyl (phenyl (thio-nitrosomethyl) silylium) orthosilicate, and 120g of 1-cyclohexyl-2-butenol were placed, followed by nitrogen purge for 60 min. After that, 0.008g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane was put into a flask, and the temperature of the flask was increased to 70 ℃, followed by stirring for 5 hours. The residual solvent was removed by distillation. After 102g of the resulting compound was introduced into 600mL of methylene chloride, 37g of triethylamine was added thereto, followed by slowly introducing 90g of acryloyl chloride while stirring at 0 ℃. The residual solvent was removed by distillation, thereby preparing a compound represented by formula 8, noted VIII. Purity 97% by HPLC, m/e: 626.32;1H NMR(400MHz，Chloroform-d)δ6.40(d,2H),δ6.05(d,2H), δ5.80(d,2H),δ4.0(m,3H),δ3.55(s,6H),δ2.47(s,6H),δ1.6(m,4H),δ1.53(m,8H),δ1.49(m,4H), 1.43(m,2H),δ1.25-1.27(m,12H)。
[ formula 8]
Figure BDA0002315518610000132
Example 9
In a 1000mL flask equipped with a cooling tube and a stirrer, 800mL of toluene and 78.6g of 3- (benzo [ c ] were placed]Thiophen-4-yl) -3-cyclohexyl-1, 1,5, 5-trimethyltrisiloxane (gukukol chemical) and 30g of allyl alcohol, followed by a nitrogen purge for 60 min. After that, 0.008g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane was put into a flask, and the temperature of the flask was increased to 70 ℃, followed by stirring for 5 hours. The residual solvent was removed by distillation. Separating by column chromatography to obtain intermediate containing single-end allyl alcohol. Then, 96g of the obtained compound was put into a three-necked flask containing 600mL of toluene, 40g of allyl (2, 2-diethoxyethyl) sulfane (Hubei Jusheng technology) was added, and then nitrogen purging was performed for 60 min. After that, 0.006g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane was put into a flask, the temperature of the flask was increased to 70 ℃, and thenStirring for 5 h. The residual solvent was removed by distillation to give a second step intermediate product, which was added to 600mL of methylene chloride, to which was added 35g of triethylamine, followed by slowly introducing 55g of methacryloyl chloride while stirring at 0 ℃. The residual solvent was removed by distillation, thereby preparing a compound represented by formula 9, designated as IX. Purity 98% by HPLC, m/e: 710.30;1H NMR(400MHz,Chloroform-d)δ7.56(d,1H),δ7.45(m,1H),δ7.20(s,2H),δ7.18(m,1H), δ6.40(d,2H),δ5.80(d,2H),δ4.47(m,1H),δ4.27(m,2H),δ3.55(m,6H),δ2.74(d,2H),δ2.44(m,2H), 2.01(m,3H),δ1.6-1.7(m,8H),δ1.5(m,4H),δ1.4(m,1H),δ1.1(t,6H),δ0.6-0.8(m,4H),δ0.20(s,12H)。
[ formula 9]
Figure BDA0002315518610000141
The details of the components used in the test comparative examples and test examples are as follows:
(A) the silicon-containing monomers of the respective test examples and test comparative examples are shown in tables 1 and 2.
(B) Photocurable diluent monomer: (B1) polyethylene glycol diglycidyl ether (PEG400) (Jiangsu Sanmu), (B2) decanediol diacrylate (Michelin)
(C) Free radical photoinitiator: 2-Isopropylthioxanthone (ITX) (Changzhou Qiangli)
(D) Cationic photoinitiator: PAG-201 (Changzhou strong)
The materials were mixed uniformly in the proportions given in table 1 and UV cured for the following tests:
cure shrinkage (%): placing the composition in a polytetrafluoroethylene mold at a rate of 100mW/cm2After UV curing at 395nm for 10 seconds, the composition was left in an oven at 60 ℃ for 1h to completely cure. After curing was complete, the length of the test specimen was measured using calipers. The cure shrinkage of the encapsulating composition was calculated according to the following equation:
curing shrinkage (%) of (| C-D |/C) × 100%
Where C is the length of the mold before curing and D is the length of the sample after UV curing.
Photocuring rate (%): at 1635cm-1(C ═ C) and 1720cm-1The intensity of an absorption peak near (C ═ O) was measured for the composition for encapsulation using FT-IR. The composition was applied to a glass substrate using a sprayer, followed by passing at 1000mW/cm2After UV curing by UV irradiation at 395nm for 10 seconds, the sample was placed in an oven at 60 ℃ for 1 hour to completely cure the sample, thereby obtaining a sample having a size of 20 cm. times.20 cm. times.3 μm (width. times. length. times. thickness). Subsequently, FT-IR was used at 1635cm-1(C ═ C) and 1720cm-1The intensity of the absorption peak of the cured film was measured in the vicinity of (C ═ O). The photocuring rate was calculated by the following equation:
the photocuring rate (%) was |1- (A/B) |. times.100%
(where A is at 1635cm as measured for the cured film-1Intensity of nearby absorption peak and at 1720cm-1The ratio of the intensities of the absorption peaks in the vicinity, and B is at 1635cm measured for the composition used for encapsulation-1The intensity of the nearby absorption peak is 1720cm-1The ratio of the intensities of the nearby absorption peaks).
And (3) adhesive force grade: the test was performed according to GB/T9286-.
Hardness: the test was performed according to GB/T6739-2006.
Viscosity (mPa · s): the viscosity of the sample was measured using a plate rheometer at a temperature of 25 ℃ and a shear rate of 10 r/s.
The test is carried out after the components are uniformly mixed according to the proportion in the table 1, and the test results are shown in tables 3 and 4:
TABLE 1
Figure BDA0002315518610000151
TABLE 2
Figure BDA0002315518610000152
Figure BDA0002315518610000161
TABLE 3
Figure BDA0002315518610000162
TABLE 4
Figure BDA0002315518610000163
Figure BDA0002315518610000171
As can be seen from the above table, the hybrid monomer of acrylate and epoxy has a higher curing rate than the simple epoxy monomer in examples 1-20 compared to comparative examples 1-2; examples 1-20 compared to comparative examples 3-4, hybrid monomers of acrylate and epoxy had lower shrinkage and higher hardness and adhesion compared to the mono-pure acrylic monomer. As can be seen from the comparison of examples 1-2, 4-6, 8-15, 17-20 and examples 3, 7, 16, the repeating unit n ═ 2 in siloxane in the silicon-containing monomer has a lower viscosity than the ink composition formed with n ═ 12, and the ink composition having a low viscosity is more suitable for the low temperature inkjet process.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
because the photocurable silicon-containing monomer component is a photocurable silicon-containing monomer or a combination of a plurality of photocurable silicon-containing monomers, the curable silicon-containing monomer with the structural formula I is used as a polymerized monomer, and in the photocurable silicon-containing monomer component, A1And A2At least one of them is represented by any one of structural formula II to structural formula IV, A1And A2At least one of which is represented by structure V. That is, the present application combines the use of monomers containing both acrylate and epoxy functionalities to form a free radical-cationic hybrid cure system when combined with a reactive diluent component. In hybrid photocuring systems, free radical monomersThe light curing rate of the system can be improved, the curing shrinkage rate of the system can be increased, and the adhesive force of the system to a base material can be reduced; and the cationic monomer can reduce the curing shrinkage of the system and improve the adhesion to the base material. The two are combined to obtain a material which integrates the advantages of the acrylic ester and the epoxy light-curable silicon-containing monomer, and the organic barrier layer with higher light curing rate, lower curing shrinkage rate and moderate substrate adhesion and hardness is realized. Thereby better satisfying the requirements of the prior art for ink-jet printing.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (13)

1. An ink composition, comprising a photocurable silicon-containing monomer component, a reactive diluent component, and a photoinitiator component, wherein the photocurable silicon-containing monomer component is a photocurable silicon-containing monomer or a combination of a plurality of photocurable silicon-containing monomers, and each of the photocurable silicon-containing monomers has the following structural formula I:
Figure FDA0002315518600000011
wherein n is any integer of 0 to 50; r1And R2Are the same or different and are each independently selected from: single bond, substituted or unsubstituted C1～C50Alkylene of (a), substituted or unsubstituted C3～C50Cycloalkylene group of (1), substituted or unsubstituted C1～C50Alkylene ether group of (A), substituted or unsubstituted C6～C50Arylene of (a), substituted or unsubstituted C7～C50Arylalkylene of (A), N- (R)3)-R4-、-O-R5-any of; wherein R is3Is hydrogen, substituted or unsubstituted C1～C50One of the alkyl groups of (1), R4Is substituted or unsubstituted C1～C50An alkylene group of (a); r5Is substituted or unsubstituted C1～C50An alkylene group of (a);
X1、X2、X3、X4are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C1～C50Alkyl, substituted or unsubstituted C1～C50Alkyl ether group of (A), substituted or unsubstituted C1～C50Cycloalkyl, substituted or unsubstituted C1～C50Alkyl sulfide group of (a), substituted or unsubstituted C6～C50Aryl, substituted or unsubstituted C3～C50Heteroaryl, substituted or unsubstituted C7～C50Aralkyl, -NR6R7Any one of the above; wherein R is6And R7Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C1～C50Any one of the alkyl groups of (a);
A1and A2Are the same or different and are each independently selected from: hydrogen, substituted or unsubstituted C1～C50Alkyl, substituted or unsubstituted C1～C60Alkyl ether group of (A), substituted or unsubstituted C1～C50Alkyl sulfide group of (a), substituted or unsubstituted C6～C50Aryl, substituted or unsubstituted C7～C50Aralkyl, -NR8R9Any one of a substituted or unsubstituted acrylate group; wherein R is8And R9Are the same or different and are each independently selected from hydrogen, substituted or unsubstituted C1～C50Any one of the alkyl groups of (a); and in the photocurable silicon-containing monomer component, the A1And said A2At least one of them is represented by any one of structural formula II to structural formula IV, A1And said A2At least one of which is represented by structural formula V:
Figure FDA0002315518600000012
wherein, denotes the binding site, Z1、Z2、Z3、Z4、Z5、Z6、Z7And Z8Each independently selected from hydrogen, substituted or unsubstituted C1～C50Any one of the alkyl groups of (1).
2. The ink composition according to claim 1, wherein n is an integer of 0 to 10, preferably R1And R2Each independently selected from: substituted or unsubstituted C1To C10Alkylene of, -O-R5Any one of-and-O-R5in-R5Is substituted or unsubstituted C1To C10One of alkylene groups of (1), preferably X1、X2、X3、X4Same or different, each independently selected from hydrogen, substituted or unsubstituted C1To C10Alkyl, substituted or unsubstituted C6To C10Aryl, substituted or unsubstituted C7To C11Any one of the aralkyl groups of (1), and X1、X2、X3、X4Is substituted or unsubstituted C6To C10Aryl, substituted or unsubstituted C7To C11Any one of the aralkyl groups of (1).
3. The ink composition as claimed in claim 1 or 2, wherein the photocurable silicon-containing monomer component is a combination of a plurality of photocurable silicon-containing monomers, wherein the A of one of the photocurable silicon-containing monomers1And A2Is a group represented by the structural formula III, preferably the Z4、Z5、Z6Each independently selected from hydrogen, substituted or unsubstituted C1To C10More preferably, the alkyl group of (a) is hydrogen.
4. The ink composition as claimed in claim 1 or 2, wherein the photocurable silicon-containing monomer component is a combination of a plurality of photocurable silicon-containing monomers, wherein the A of one of the photocurable silicon-containing monomers1And A2Is a group represented by the structural formula V, preferably Z8Selected from hydrogen, substituted or unsubstituted C1To C10More preferably, the alkyl group of (1) is a methyl group.
5. The ink composition as claimed in claim 1 or 2, wherein the A of at least one of the photocurable silicon-containing monomers of the photocurable silicon-containing monomer component1Is a group represented by the structural formula V, and the A2Is a group represented by the structural formula III; preferably said Z8Selected from hydrogen, substituted or unsubstituted C1To C10Any of the alkyl groups of (a), more preferably methyl; preferably said Z4、Z5、Z6Each independently selected from hydrogen, substituted or unsubstituted C1To C10More preferably, the alkyl group of (a) is hydrogen.
6. The ink composition of claim 1, wherein the reactive diluent component is any one or more of photocurable diluent monomers having one or more functional groups of 1 to 4 epoxy or oxetane groups, (meth) acryloxy groups, preferably the reactive diluent monomer has a structure represented by formula VI:
Figure FDA0002315518600000021
wherein Y is selected from: single bond, substituted or unsubstituted C1To C50Alkylene of (a), substituted or unsubstituted C3To C50Cycloalkylene group of (1), substituted or unsubstituted C1To C50Alkylene ether group of (A), substituted or unsubstituted C6To C50Arylene of (a)Substituted or unsubstituted C7To C50Arylalkylene of-O-R10-、-N(R11)-R12-any of; wherein R is10Selected from substituted or unsubstituted C1To C50Any one of alkylene groups; r11Is hydrogen, substituted or unsubstituted C1To C50Any one of alkyl, R12Is substituted or unsubstituted C1To C50Any one of alkylene groups; z9、Z10Each independently selected from hydrogen, substituted or unsubstituted C1～C50Alkyl, substituted or unsubstituted C1～C60And Z is any one of an alkyl ether group, a substituted or unsubstituted acrylate group9、Z10Is represented by any one of formula II, formula III, formula IV, formula V; more preferably, the reactive diluent component comprises at least two photocurable diluent monomers, and each of the two photocurable diluent monomers is independently of the structure of formula VI, and wherein Z of one of the photocurable diluent monomers9And Z10Each independently being a (meth) acryloyloxy group, Z of another of said photocurable diluent monomers9And Z10Each independently is one of 1 to 4 epoxy groups or oxetane groups.
7. The ink composition of claim 6, wherein Y is selected from substituted or unsubstituted C1To C10Alkylene, substituted or unsubstituted C1To C10Alkylene ether group, substituted or unsubstituted C6To C10Arylene, substituted or unsubstituted C7To C11Any one of arylalkylene groups.
8. The ink composition of claim 1, wherein the photoinitiator component comprises a free radical photoinitiator and a cationic photoinitiator, preferably wherein the free radical photoinitiator is one or more of a benzoin-based free radical photoinitiator, a benzil-based free radical photoinitiator, an alkyl phenone-based free radical photoinitiator, an acyl phosphorous oxide-based free radical photoinitiator, a benzophenone-based free radical photoinitiator, and a thioxanthone-based free radical photoinitiator, preferably, the cationic photoinitiator is one or more of a diaryliodonium salt cationic photoinitiator, a triarylsulfonium salt cationic photoinitiator, a diazonium salt cationic photoinitiator, an alkylsulfonium salt cationic photoinitiator, an iron arene salt cationic photoinitiator, a sulfonyloxy ketone cationic photoinitiator, and a triarylsiloxy ether cationic photoinitiator.
9. The ink composition of claim 1, wherein the ink composition comprises, by weight, 5 to 90% of the photocurable silicon-containing monomer component, 5 to 90% of the reactive diluent component, and 0.02 to 20% of the photoinitiator component, wherein the cationic photoinitiator and the free-radical photoinitiator in the photoinitiator component are each independently 0.01 to 10%; preferably, the content of the photocurable silicon-containing monomer component is 20-50%, the content of the reactive diluent component is 40-80%, and the content of the cationic photoinitiator and the content of the free radical photoinitiator are respectively and independently 1-8%.
10. The ink composition as claimed in claim 1, wherein the ink composition further comprises an auxiliary component, preferably the auxiliary component is selected from any one or more of a polymerization inhibitor, a surfactant, an antioxidant, a defoaming agent and a leveling agent, and preferably the auxiliary component is contained in an amount of 0.01 to 5 wt%.
11. The ink composition according to claim 1, wherein the viscosity of the ink composition at 25 ℃ is 1 to 50 mPa-s.
12. An encapsulation structure comprising an organic layer, wherein the organic layer is formed by photocuring using the ink composition according to any one of claims 1 to 11.
13. A semiconductor device comprising a functional structure and an encapsulation structure, wherein the encapsulation structure is the encapsulation structure of claim 12, preferably wherein the semiconductor device is any one of an electroluminescent device, a photoluminescent device, a lighting device, a light emitting diode, a solar cell, a thin film transistor, and a photodetector.
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CN113185544A (en) * 2021-05-25 2021-07-30 吉林奥来德光电材料股份有限公司 Compound for packaging film, ink composition containing compound and packaging structure
CN115109462A (en) * 2022-07-06 2022-09-27 杭州福斯特应用材料股份有限公司 Photocuring composition, packaging method, packaging structure and semiconductor device
CN115353587A (en) * 2022-09-20 2022-11-18 浙江福斯特新材料研究院有限公司 Application of cyclopentane trimer substituent, photocuring composition, organic packaging film and OLED device
CN116162201A (en) * 2022-12-20 2023-05-26 浙江福斯特新材料研究院有限公司 Photocurable encapsulation composition, encapsulation method, encapsulation structure and semiconductor device
WO2024007741A1 (en) * 2022-07-06 2024-01-11 杭州福斯特应用材料股份有限公司 Ink composition, packaging structure, and semiconductor device

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