CN116478650A - Normal-temperature high-modulus ultraviolet impression compound and preparation method thereof - Google Patents
Normal-temperature high-modulus ultraviolet impression compound and preparation method thereof Download PDFInfo
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- CN116478650A CN116478650A CN202310471266.3A CN202310471266A CN116478650A CN 116478650 A CN116478650 A CN 116478650A CN 202310471266 A CN202310471266 A CN 202310471266A CN 116478650 A CN116478650 A CN 116478650A
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- 150000001875 compounds Chemical class 0.000 title claims description 30
- 238000002360 preparation method Methods 0.000 title abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 49
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 20
- 239000000853 adhesive Substances 0.000 claims abstract description 19
- 230000001070 adhesive effect Effects 0.000 claims abstract description 19
- 239000004814 polyurethane Substances 0.000 claims abstract description 19
- 229920002635 polyurethane Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- 239000003292 glue Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 238000004049 embossing Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 16
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 12
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 12
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 12
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 claims description 11
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 5
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 claims description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 3
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 3
- FFFHGDCIVMQLBJ-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;prop-1-ene Chemical compound CC=C.CC=C.OC(=O)C1=CC=CC(C(O)=O)=C1 FFFHGDCIVMQLBJ-UHFFFAOYSA-N 0.000 claims 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims 1
- OLCMZGLZCSAMRF-UHFFFAOYSA-N phthalic acid;prop-1-ene Chemical compound CC=C.CC=C.OC(=O)C1=CC=CC=C1C(O)=O OLCMZGLZCSAMRF-UHFFFAOYSA-N 0.000 claims 1
- -1 acrylic ester Chemical class 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 16
- 238000003860 storage Methods 0.000 abstract description 10
- 238000004132 cross linking Methods 0.000 abstract description 6
- 238000001723 curing Methods 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000000016 photochemical curing Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 239000012949 free radical photoinitiator Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 11
- 239000006087 Silane Coupling Agent Substances 0.000 description 10
- FAKJFAMIABOKBW-UHFFFAOYSA-N 1-(2,4-dichloro-5-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC(F)=C(Cl)C=C1Cl FAKJFAMIABOKBW-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 101100115801 Streptomyces mobaraensis daip gene Proteins 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- FZNKCFJDFGDMKU-UHFFFAOYSA-N dipropyl benzene-1,3-dicarboxylate Chemical compound CCCOC(=O)C1=CC=CC(C(=O)OCCC)=C1 FZNKCFJDFGDMKU-UHFFFAOYSA-N 0.000 description 5
- 239000004641 Diallyl-phthalate Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001015 X-ray lithography Methods 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 2
- 238000000609 electron-beam lithography Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- VSLIZFRORGVSOU-UHFFFAOYSA-N 2,4-dichloro-n-[3-cyano-6-[(4-hydroxyphenyl)methyl]-5,7-dihydro-4h-thieno[2,3-c]pyridin-2-yl]-5-morpholin-4-ylsulfonylbenzamide Chemical compound C1=CC(O)=CC=C1CN1CC(SC(NC(=O)C=2C(=CC(Cl)=C(C=2)S(=O)(=O)N2CCOCC2)Cl)=C2C#N)=C2CC1 VSLIZFRORGVSOU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- IQTAKJQIVCHRKC-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C1=CC(C(=O)O)=CC=C1)(=O)O Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C1=CC(C(=O)O)=CC=C1)(=O)O IQTAKJQIVCHRKC-UHFFFAOYSA-N 0.000 description 1
- 238000000018 DNA microarray Methods 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a normal-temperature high-modulus ultraviolet embossing adhesive and a preparation method thereof, wherein the embossing adhesive comprises the following raw material components in parts by weight: 5-15 parts of rigid acrylate oligomer, 10-30 parts of hyperbranched polyester acrylate oligomer, 5-20 parts of polyurethane acrylate, 20-60 parts of reactive diluent, 1-9 parts of photoinitiator and 1-3 parts of auxiliary agent. The imprinting adhesive of the invention introduces acrylate oligomer with a rigid group or a structural unit, and the rigid group or the structural unit endows the photocuring film with extremely high storage modulus, so that the anti-damage capability of the ultraviolet imprinting adhesive material structure in demolding in the imprinting process is improved; the reactive diluent of the acrylic ester with two to four functions is selected, and the reactive diluent is matched with hyperbranched polyester, so that the curing and crosslinking density of the system is improved, and the low viscosity of the system ensures the application of the imprinting glue in an imprinting process; the high-activity free radical photoinitiator is matched for use, so that the photo-curing speed of the body is further improved, and excellent optical performance is provided.
Description
Technical Field
The invention relates to the technical field of preparation of imprinting glue, in particular to normal-temperature high-modulus ultraviolet imprinting glue and a preparation method thereof.
Background
Micro-nano manufacturing technology is an important support of modern micro-nano technology industry and is the manufacturing basis of integrated circuits, photoelectric devices and micro-electromechanical systems. In recent years, with the continuous expansion of the application field of micro-nano manufacturing and the continuous development of micro-nano optics and photonics, the requirements of augmented reality, multi-information optical detection, optical sensors, super-structured materials, biochips and the like on large-area micro-nano patterning devices are increasing, and the performances of the micro-nano devices are related to the microstructure of the material surface, and the microstructure of the micro-nano devices can be generally prepared by utilizing technologies such as electron beam lithography, deep ultraviolet to X-ray lithography and the like. However, the electron beam lithography technology is difficult to be applied to large-area pattern manufacture and industrial production due to expensive equipment and low efficiency; deep ultraviolet to X-ray lithography requirements are complex, lithography equipment is expensive, and high-energy radiation can adversely affect material properties, limiting the application of the material. Compared with the prior art, the large-area nanoimprint technology can efficiently manufacture large-area and complex three-dimensional micro-nano structures on a large-size non-flat rigid substrate or a fragile substrate at low cost, and is a key for mass and large-scale manufacture of micro-nano devices. Therefore, development of large area nanoimprint technology is always an important research direction in industry.
The large-area nano imprinting technology relates to elements such as imprinting equipment, imprinting materials, imprinting templates, imprinting technology and the like, wherein the imprinting materials (imprinting glue) are used as key materials for patterning in the nano imprinting process, and have very important influences on the efficiency, the precision and the quality of imprinting patterns of large-area nano imprinting. The large-area nano imprinting technology requires that the imprinting glue has the following basic performance requirements: (1) high curing speed; (2) The coating method is suitable for large-area coating modes such as slit coating, spraying and the like; (3) can be stamped in normal temperature and atmospheric environment; (4) high adhesion to the substrate; (5) the mold is suitable for large-area micro-nano structure demolding; and (6) realizing the rapid and complete filling of the large-area micro-nano structure. In addition, due to different applications of the manufactured device, not only is proper selection of the type of the imprint adhesive needed, but also some customization demands are put on the property of the imprint adhesive. Materials (polyimide, metal oxide-based imprint gels) that require low absorption, high refractive index, and radiation stability for optical applications; some three-dimensional structures are embossed, and specific requirements are set on mechanical properties (Young's modulus and hardness) of the cured embossing adhesive in order to prevent structural damage during demolding. However, most of the nano imprinting adhesives at present cannot meet the specific performance requirements of large-area nano imprinting at the same time, so that new imprinting adhesive materials are still required to be continuously developed to meet different device applications.
Aiming at the problem that when some three-dimensional structures are stamped, the structures are damaged due to overlarge demolding force in the demolding process due to the fine feature size requirement of high aspect ratio. The Philips institute and SUSS Micro Tec company propose a substrate conformal nanoimprint technology which can prepare sub-10 nm structures on a wafer, and the diameter of the imprinted substrate can reach 200mm, and the technology sequentially and continuously imprints, and makes imprinting glue enter a template by virtue of capillary force, so that the generation of bubbles in the imprinting process and the damage to the structures in the demolding process can be reduced. Nithi et al of Morphotonis utilize large area roll-to-plate ultraviolet cured nanoimprinting to prepare high aspect ratio microstructures with superhydrophobic and oleophobic properties on flexible substrates, and achieve small release forces to avoid structural damage by improving the imprinting process. However, in the prior art, damage to the micro-nano structure caused by the imprinting process is reduced by improving the imprinting process, imprinting equipment, template materials and the like, and technical reports about improvement of the storage modulus of an imprinting adhesive cured film and thus improvement of the demolding resistance of the imprinting structure are not seen at present, and the existing imprinting adhesive material can not meet the manufacturing requirements of some specific three-dimensional structures.
Disclosure of Invention
The invention aims to solve the technical problem of providing the normal-temperature high-modulus ultraviolet stamping adhesive and the preparation method thereof aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme: the normal-temperature high-modulus ultraviolet embossing adhesive comprises the following raw material components in parts by weight: 5-15 parts of rigid acrylate oligomer, 10-30 parts of hyperbranched polyester acrylate oligomer, 5-20 parts of polyurethane acrylate, 20-60 parts of reactive diluent, 1-9 parts of photoinitiator and 1-3 parts of auxiliary agent.
Preferably, the rigid acrylate oligomer is one or two of diallyl phthalate and diallyl isophthalate.
Preferably, the hyperbranched polyester acrylate oligomer is one or two of oligomer CN2303NS and oligomer CN 2304.
Preferably, the polyurethane acrylate is one or two of CN8885NS and CN983 NS.
Preferably, the reactive diluent is one or more of a difunctional acrylate monomer, a trifunctional acrylate monomer and a tetrafunctional acrylate monomer.
Preferably, the difunctional acrylate monomer is selected from one or more of 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and diethylene glycol dimethacrylate.
Preferably, the trifunctional acrylate monomer is selected from one or more of trimethylolpropane triacrylate, glycerol triacrylate, and trimethylolpropane triacrylate.
Preferably, the tetrafunctional acrylate monomer is selected from one or two of pentaerythritol tetraacrylate and di-trimethylolpropane tetraacrylate.
Preferably, the photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide;
the auxiliary agent comprises one or more of a coupling agent, a defoaming agent and a leveling agent.
The invention also provides a preparation method of the normal-temperature high-modulus ultraviolet stamping adhesive, which comprises the following steps: according to the weight proportion, 5-15 parts of rigid acrylate oligomer, 10-30 parts of hyperbranched polyester acrylate oligomer, 5-20 parts of polyurethane acrylate, 20-60 parts of reactive diluent, 1-9 parts of photoinitiator and 1-3 parts of auxiliary agent are uniformly mixed in a light-proof environment, and the normal-temperature high-modulus ultraviolet impression compound is obtained.
The beneficial effects of the invention are as follows:
the normal-temperature high-modulus ultraviolet stamping adhesive provided by the invention has excellent performance, has the characteristics of low viscosity, low shrinkage, high oxidation resistance, high hardness, high glossiness, no yellowing and the like, and simultaneously has very high storage modulus at normal temperature, so that the defects of the existing stamping adhesive material in manufacturing of some specific three-dimensional structures are overcome;
according to the invention, the acrylate oligomer with the rigid group or the structural unit is introduced, the rigid group or the structural unit endows the photo-curing film with extremely high storage modulus, and the anti-damage capability of the ultraviolet imprinting adhesive material structure in the demolding process of the imprinting process is improved;
in the imprinting glue, the two-to-four-functional acrylate reactive diluent is selected, and hyperbranched polyester is matched, so that the curing and crosslinking density of the system is improved, and the low viscosity of the system ensures the application of the imprinting glue in an imprinting process;
the high-activity free radical photoinitiator is matched for use, so that the photo-curing speed of the body is further improved, and excellent optical performance is provided.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides normal-temperature high-modulus ultraviolet impression compound, which comprises the following raw material components in parts by weight: 5-15 parts of rigid acrylate oligomer, 10-30 parts of hyperbranched polyester acrylate oligomer, 5-20 parts of polyurethane acrylate, 20-60 parts of reactive diluent, 1-9 parts of photoinitiator and 1-3 parts of auxiliary agent.
Wherein the rigid acrylate oligomer is an acrylate containing rigid groups or structural units to impart a very high rigidity to the system, in preferred embodiments one or both of the diacrylates DAP, DAIP.
Wherein the hyperbranched polyester acrylate oligomer is one or two of oligomer CN2303NS and oligomer CN2304, so as to ensure high photo-curing rate and increase the molecular weight of the system at the same time, thereby providing larger modulus.
Wherein, the polyurethane acrylic ester is one or two of CN8885NS and CN983NS, and the addition of the polyurethane acrylic ester can further increase the crosslinking degree of the system and improve the elasticity and the toughness.
Wherein the reactive diluent is one or a mixture of two or more of low-viscosity, high-dilutability and low-volatility acrylate monomers with four functionalities. Too low a functionality results in a low system strength and too high a volatility results in a too high cure speed resulting in a low molecular weight and weakening of the system strength. The reactive diluents of the present invention can achieve suitable overall properties.
In preferred embodiments, the difunctional acrylate monomer is selected from one or more of 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol dimethacrylate, which promotes branching or crosslinking of the system to increase strength.
In a preferred embodiment, the trifunctional acrylate monomer is selected from one or more of trimethylolpropane triacrylate, glycerol triacrylate, trimethylolpropane triacrylate, which can increase the cross-linking density and cure speed of the system, as well as hydrophobicity.
In a preferred embodiment, the tetrafunctional acrylate monomer is selected from one or both of pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, which can further increase the crosslink density and cure speed.
Wherein the photoinitiator is selected from one or more of 1-hydroxy cyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone and 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide;
wherein the auxiliary agent comprises one or more of a coupling agent, a defoaming agent and a leveling agent. In a preferred embodiment, the auxiliary agent comprises a coupling agent, a leveling agent, the coupling agent being a silane coupling agent, more preferably KH560. The leveling agent is preferably DCFA4 or MONENG-1153.
The invention also provides a preparation method of the normal-temperature high-modulus ultraviolet impression compound, which comprises the following steps: according to the weight ratio, under clean, low-humidity and light-shielding environment, 5-15 parts of rigid acrylic ester oligomer, 10-30 parts of hyperbranched polyester acrylic ester oligomer, 5-20 parts of polyurethane acrylic ester, 20-60 parts of reactive diluent, 1-9 parts of photoinitiator and 1-3 parts of auxiliary agent are uniformly mixed, and the normal-temperature high-modulus ultraviolet impression compound is obtained.
The foregoing is a general inventive concept and the following detailed examples and comparative examples are provided on the basis thereof to further illustrate the invention.
The sources of some of the raw materials in the following examples are as follows:
branched polyester acrylates (CN 2303NS, CN 2304), sardola; polyurethane acrylates (CN 983, CN 8885), sardola; tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, sartomer;
1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, IGM;
silane coupling agent (KH 560), IGM; difunctional fluoroacrylate (DCFA 4) leveling agent, aldrich.
Example 1
The preparation method of the normal-temperature high-modulus ultraviolet impression compound comprises the following steps:
under clean, low-humidity and light-shading environment, accurately weighing 5 parts of isophthalic acid dipropyl ester DAIP, 20 parts of hyperbranched polyester acrylic ester CN2303NS, 15 parts of polyurethane acrylic ester CN8885NS, 50 parts of tricyclodecane dimethanol diacrylate, 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 5.5 parts of 1-hydroxycyclohexyl phenyl ketone, 1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 1 part of silane coupling agent KH-560 and 0.5 part of DCFA, and fully and uniformly mixing to obtain the normal-temperature high-modulus ultraviolet impression compound.
Example 2
The preparation method of the normal-temperature high-modulus ultraviolet impression compound comprises the following steps:
under clean, low-humidity and light-resistant environment, accurately weighing 10 parts of isophthalic acid dipropyl ester DAIP, 15 parts of hyperbranched polyester acrylic ester CN2303NS, 15 parts of polyurethane acrylic ester CN983NS, 50 parts of trimethylolpropane triacrylate, 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 5.5 parts of 1-hydroxycyclohexyl phenyl ketone, 1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 1 part of silane coupling agent KH-560 and 0.5 part of DCFA, and fully and uniformly mixing to obtain the normal-temperature high-modulus ultraviolet impression compound.
Example 3
The preparation method of the normal-temperature high-modulus ultraviolet impression compound comprises the following steps:
under clean, low-humidity and light-shading environment, accurately weighing 10 parts of phthalic acid dipropyl ester DAP, 10 parts of hyperbranched polyester acrylic ester CN2303NS, 20 parts of polyurethane acrylic ester CN8885NS, 50 parts of tricyclodecane dimethanol diacrylate, 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 5.5 parts of 1-hydroxycyclohexyl phenyl ketone, 1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 1 part of silane coupling agent KH-560 and 0.5 part of DCFA, and fully and uniformly mixing to obtain the normal-temperature high-modulus ultraviolet impression compound.
Example 4
The preparation method of the normal-temperature high-modulus ultraviolet impression compound comprises the following steps:
under clean, low-humidity and light-shading environment, accurately weighing 5 parts of diallyl phthalate DAIP, 25 parts of hyperbranched polyester acrylate CN2303NS, 10 parts of polyurethane acrylate CN983NS, 30 parts of tricyclodecane dimethanol diacrylate, 20 parts of trimethylolpropane triacrylate, 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 5.5 parts of 1-hydroxycyclohexyl phenyl ketone, 1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone, 1 part of silane coupling agent KH-560 and 40.5 parts of DCFA, and fully and uniformly mixing to obtain the ultraviolet imprinting adhesive with normal temperature and high modulus.
Example 5
The preparation method of the normal-temperature high-modulus ultraviolet impression compound comprises the following steps:
under clean, low-humidity and light-shading environment, accurately weighing 10 parts of isophthalic acid diacrylate DAIP, 20 parts of hyperbranched polyester acrylic ester CN2303NS, 10 parts of polyurethane acrylic ester CN8885NS, 30 parts of tricyclodecane dimethanol diacrylate, 20 parts of pentaerythritol tetraacrylate, 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 5.5 parts of 1-hydroxycyclohexyl phenyl ketone, 1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone, 1 part of silane coupling agent KH-560 and 0.5 part of DCFA, and fully and uniformly mixing to obtain the ultraviolet impression compound with normal temperature and high modulus.
Comparative example 1
The preparation method of the normal-temperature high-modulus ultraviolet impression compound comprises the following steps:
under clean, low-humidity and light-shading environment, accurately weighing 3 parts of isophthalic acid dipropyl ester DAIP, 3 parts of hyperbranched polyester acrylic ester CN2303NS 22 parts of polyurethane acrylic ester CN8885NS 15 parts, 50 parts of tricyclodecane dimethanol diacrylate, 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 5.5 parts of 1-hydroxycyclohexyl phenyl ketone, 1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 1 part of silane coupling agent KH-560 and 0.5 part of DCFA, and fully and uniformly mixing to obtain the normal-temperature high-modulus ultraviolet impression compound.
Comparative example 2
The preparation method of the normal-temperature high-modulus ultraviolet impression compound comprises the following steps:
under clean, low-humidity and light-shading environment, 17 parts of isophthalic acid dipropyl ester DAIP, 3NS 8 parts of hyperbranched polyester acrylic ester CN 2305 NS 15 parts of polyurethane acrylic ester CN8885, 50 parts of tricyclodecane dimethanol diacrylate, 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 5.5 parts of 1-hydroxycyclohexyl phenyl ketone, 1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 1 part of silane coupling agent KH-560 and 0.5 part of DCFA are accurately weighed according to parts by weight, and fully and uniformly mixed to obtain the normal-temperature high-modulus ultraviolet impression compound.
Comparative example 3
The preparation method of the normal-temperature high-modulus ultraviolet impression compound comprises the following steps:
under clean, low-humidity and light-shading environment, 15 parts of isophthalic acid dipropyl ester DAIP, 25 parts of polyurethane acrylic ester CN8885NS, 50 parts of tricyclodecane dimethanol diacrylate, 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 5.5 parts of 1-hydroxycyclohexyl phenyl ketone, 1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 1 part of silane coupling agent KH-560 and 0.5 part of DCFA are accurately weighed according to parts by weight, and are fully and uniformly mixed to obtain the normal-temperature high-modulus ultraviolet impression compound.
For the ultraviolet impression compounds prepared in the above examples 1 to 5 and comparative examples 1 to 3, the corresponding properties were tested using the apparatus/method shown in the following table 1 and the results were recorded:
TABLE 1
| Test item | Viscosity of the mixture | Shrinkage rate | Storage modulus | Hardness of |
| Test method | Viscometer (viscosimeter) | Density method | DMA | Pencil hardness tester |
The test results are shown in table 2 below:
TABLE 2
From the above results, it is clear that comparative example 1 has a lower storage modulus and a lower hardness, and the key performance is lowered due to the fact that the amount of the acrylate oligomer containing the rigid group or the structural unit added into the system is small, and the rigidity of the system is not sufficiently contributed; the storage modulus of the comparative example 2 and the storage modulus of the comparative example 3 are also lower, and the viscosity is also higher, and the dilution capacity of the diluent is weakened due to the excessive addition of the components of the rigid acrylate oligomer, so that the viscosity of the system is higher; meanwhile, the ultraviolet imprinting glue does not contain hyperbranched polyester acrylic ester or has too little content, so that the curing crosslinking density of the ultraviolet imprinting glue with high modulus at normal temperature cannot be improved, and the storage modulus of the imprinting glue curing film is lower.
The imprinting glue prepared by the embodiments 1-5 of the invention has excellent performances, has the characteristics of low viscosity, low shrinkage, high oxidation resistance, high hardness, high glossiness, no yellowing and the like, and the cured film after curing also has high storage modulus at normal temperature, so that the defects of the existing imprinting glue material in the preparation of specific three-dimensional structures are overcome.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. The normal-temperature high-modulus ultraviolet embossing adhesive is characterized by comprising the following raw material components in parts by weight: 5-15 parts of rigid acrylate oligomer, 10-30 parts of hyperbranched polyester acrylate oligomer, 5-20 parts of polyurethane acrylate, 20-60 parts of reactive diluent, 1-9 parts of photoinitiator and 1-3 parts of auxiliary agent.
2. The room temperature high modulus uv impression compound according to claim 1, wherein said rigid acrylate oligomer is one or both of dipropylene phthalate and dipropylene isophthalate.
3. The normal temperature high modulus ultraviolet imprinting glue according to claim 1, wherein the hyperbranched polyester acrylate oligomer is one or two of oligomer CN2303NS and oligomer CN 2304.
4. The room temperature high modulus uv impression compound according to claim 1, wherein said urethane acrylate is one or both of CN8885NS, CN983 NS.
5. The room temperature high modulus uv impression compound according to claim 1, wherein said reactive diluent is one or more of a mixture of di-functional acrylate monomers, tri-functional acrylate monomers, tetra-functional acrylate monomers.
6. The uv impression compound according to claim 5, wherein said difunctional acrylate monomer is selected from one or more of 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and diethylene glycol dimethacrylate.
7. The uv impression compound according to claim 5, wherein said trifunctional acrylate monomer is selected from one or more of trimethylolpropane triacrylate, glycerol triacrylate, trimethylolpropane triacrylate.
8. The room temperature high modulus uv impression compound according to claim 5, wherein said tetrafunctional acrylate monomer is selected from one or two of pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate.
9. The high modulus uv impression compound according to claim 1, wherein said photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide;
the auxiliary agent comprises one or more of a coupling agent, a defoaming agent and a leveling agent.
10. A method for preparing the normal-temperature high-modulus ultraviolet imprinting glue according to any one of claims 1 to 9, wherein the method comprises the following steps: according to the weight proportion, 5-15 parts of rigid acrylate oligomer, 10-30 parts of hyperbranched polyester acrylate oligomer, 5-20 parts of polyurethane acrylate, 20-60 parts of reactive diluent, 1-9 parts of photoinitiator and 1-3 parts of auxiliary agent are uniformly mixed in a light-proof environment, and the normal-temperature high-modulus ultraviolet impression compound is obtained.
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| CN117471852A (en) * | 2023-11-02 | 2024-01-30 | 璞璘材料科技(绍兴)有限公司 | Inkjet type nano-imprinting adhesive for semiconductor manufacturing and preparation method thereof |
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| CN117471852A (en) * | 2023-11-02 | 2024-01-30 | 璞璘材料科技(绍兴)有限公司 | Inkjet type nano-imprinting adhesive for semiconductor manufacturing and preparation method thereof |
| CN117471852B (en) * | 2023-11-02 | 2024-05-14 | 璞璘材料科技(绍兴)有限公司 | Inkjet type nano-imprinting adhesive for semiconductor manufacturing and preparation method thereof |
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