阅读说明：本技术 一种uv喷墨打印用油墨 (UV ink-jet printing ink ) 是由 黄时雨 高建鑫 张燕红 张兵 向文胜 赵建龙 于 2021-09-15 设计创作，主要内容包括：本发明公开了一种UV喷墨打印用油墨,以重量份数计,其包括有机硅改性聚酯丙烯酸酯齐聚物5-30份、脂肪族聚氨酯丙烯酸酯齐聚物3-20、稀释单体20-80份和光引发剂2-5份、助剂0.5-5份；所述有机硅改性聚酯丙烯酸酯齐聚物所含丙烯酸酯官能团数为1-3个；所述脂肪族聚氨酯丙烯酸酯齐聚物所含丙烯酸酯官能团数为2-6个；所述稀释单体为单官能团、双官能团、多官能团中的一种或多种,且包括长链脂肪族或含有苯环取代的丙烯酸酯和/或甲基丙烯酸酯。本发明提供的UV喷墨打印用油墨具有高柔韧性、高透光率、高光固化率等特点。(The invention discloses ink for UV ink-jet printing, which comprises 5-30 parts of organic silicon modified polyester acrylate oligomer, 3-20 parts of aliphatic polyurethane acrylate oligomer, 20-80 parts of diluent monomer, 2-5 parts of photoinitiator and 0.5-5 parts of auxiliary agent by weight; the number of acrylate functional groups contained in the organic silicon modified polyester acrylate oligomer is 1-3; the number of the acrylate functional groups contained in the aliphatic polyurethane acrylate oligomer is 2-6; the diluting monomer is one or more of monofunctional group, bifunctional group and polyfunctional group, and comprises long-chain aliphatic or acrylate and/or methacrylate containing benzene ring substitution. The UV ink-jet printing ink provided by the invention has the characteristics of high flexibility, high light transmittance, high light curing rate and the like.)

1. An ink for UV inkjet printing, characterized in that: the organic silicon modified polyester acrylate oligomer comprises, by weight, 5-30 parts of an organic silicon modified polyester acrylate oligomer, 3-20 parts of an aliphatic polyurethane acrylate oligomer, 20-80 parts of a diluent monomer, 2-5 parts of a photoinitiator and 0.5-5 parts of an auxiliary agent; the number of acrylate functional groups contained in the organic silicon modified polyester acrylate oligomer is 1-3; the number of the acrylate functional groups contained in the aliphatic polyurethane acrylate oligomer is 2-6; the diluting monomer is one or more of monofunctional group, bifunctional group and polyfunctional group, and comprises long-chain aliphatic or acrylate and/or methacrylate containing benzene ring substitution.

2. The UV inkjet printing ink of claim 1, wherein: the surface tension of the organic silicon modified polyester acrylate oligomer is 5-45mN/m, and the viscosity is 30-500 mPa.

3. The UV inkjet printing ink of claim 1, wherein: the elongation of the aliphatic polyurethane acrylate oligomer is 100-900%.

4. The UV inkjet printing ink of claim 1, wherein: the diluting monomer comprises any one or the combination of at least two of methyl acrylate, butyl acrylate, ethyl acrylate, n-butyl acrylate, octadecyl acrylate, alkoxy dodecyl acrylate, 2-phenoxyethyl methacrylate, 1, 12-dodecanediol diacrylate, 1, 6-hexanediol diacrylate, ethoxylated nonyl phenol acrylate and the like.

5. The UV ink jet printing ink of claim 4, wherein: the photoinitiator comprises any one or the combination of at least two of benzoin photoinitiators, alkyl ketone photoinitiators, acyl phosphorus oxide photoinitiators or anthrone photoinitiators.

6. The UV inkjet printing ink of claim 1, wherein: the auxiliary agent comprises any one or the combination of at least two of a leveling agent, a defoaming agent or a film-forming auxiliary agent.

[ technical field ] A method for producing a semiconductor device

The invention belongs to the technical field of jet printing ink, and particularly relates to ink for UV ink-jet printing.

[ background of the invention ]

Organic Light-Emitting diodes (OLEDs), also known as Organic Light-Emitting semiconductors, are important technologies in the field of optoelectronic display, wherein a thin film packaging technology is required for flexible OLEDs to achieve good flexibility. At present, the ink-jet printing technology has obtained large-scale manufacturing application in the preparation of an organic layer packaged by a flexible OLED film, and the application not only brings market opportunity for the ink-jet printing technology, but also continuously promotes the ink-jet printing technology to become a new microelectronic manufacturing process which is more environment-friendly and popular.

The OLED packaging aims to isolate the light-emitting device from the environment, prevent 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.

The thin film encapsulation is to grow a single-layer or multi-layer thin film on the prepared OLED device substrate so as to realize 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. In the three-layer structure, the first inorganic layer (SiNX) is a smooth substrate, the organic polymer buffer layer is obtained on the substrate through ink-jet printing and then curing, and the third inorganic layer (SiNX) is the last inorganic layer.

The organic polymer buffer layer (organic ultraviolet light curing resin) is considered to be a conventional and effective packaging material due to its characteristics of good curing property, stability, adhesive strength, transmittance, high purity and the like. In the prior art, patent No. CN201410009204 discloses an organic electroluminescent display device with a thin film encapsulation structure and a preparation method thereof, wherein an organic polymer buffer layer comprises acrylic resin, methacrylic resin, isoprene resin, vinyl resin, epoxy resin, polyurethane resin, cellulose resin, perylene resin, imide resin or a mixture of two or more resins. In general, the heat resistance of the organic layer must be maintained at 100 ℃ for reliability of the organic light emitting device. However, during a long period of high-temperature exposure, a phenomenon in which the organic layer and the inorganic layer are peeled off may occur.

Kateeva proposed an ink composition of di-and monomethacrylates in TW201723104, but no relevant data reported in its OLED devices such as stability data against water and oxygen was seen.

A ink composition of silicone modified acrylates was proposed by samsung SDI gmbh in TW 201538596. 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 composition to satisfy the performance indexes such as high flexibility, high light transmittance and fast photocuring speed, which are required by the increasing film packaging.

Therefore, there is a need to provide a new ink for UV inkjet printing to solve the above technical problems.

[ summary of the invention ]

The invention mainly aims to provide the UV ink-jet printing ink which effectively blocks water vapor and oxygen, solves the problems of poor film forming property and interface matching property of an OLED packaging material, and has the advantages of high flexibility, high light transmittance, high photocuring speed and the like.

The invention realizes the purpose through the following technical scheme: the UV ink-jet printing ink comprises, by weight, 5-30 parts of an organic silicon modified polyester acrylate oligomer, 3-20 parts of an aliphatic polyurethane acrylate oligomer, 20-80 parts of a diluent monomer, 2-5 parts of a photoinitiator and 0.5-5 parts of an auxiliary agent.

The organic silicon modified polyester acrylate oligomer may be present in an amount of 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts, the aliphatic polyurethane acrylate oligomer may be present in an amount of 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 20 parts, the diluent monomer may be present in an amount of 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts or 80 parts, the photoinitiator may be present in an amount of 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, the auxiliary may be present in an amount of 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, but not limited to the above-listed values, and other values in the above-mentioned range may be equally applicable.

Through the compounding and synergistic effect of the organic silicon modified polyester acrylate oligomer, the aliphatic polyurethane acrylate oligomer and the diluent monomer, the flexibility, the light transmittance and the photocuring rate of the UV ink-jet printing ink are obviously improved.

The invention selects the organic silicon modified polyester acrylate oligomer with 1-3 acrylate functional groups, the aliphatic polyurethane acrylate oligomer with 2-6 acrylate functional groups, the long-chain aliphatic or the diluted monomer containing the acrylic ester and/or the methacrylic ester substituted by benzene ring as the main raw materials, and prepares the jet printing ink by limiting the proportioning of the parts by quantity, thereby improving the flexibility, the light transmittance and the photocuring rate of the ink. The main resin is organic silicon modified polyester acrylate oligomer and aliphatic polyurethane acrylate oligomer, the two kinds of acrylic resin have high photocuring speed, and meanwhile, the organic silicon modified acrylic resin has excellent weather resistance and the aliphatic polyurethane acrylic resin has high flexibility. The long-chain aliphatic or benzene ring substituted acrylate/methacrylate is used as a diluting monomer, the viscosity and the surface tension of the whole ink are regulated and controlled according to the using amount of the main resin part, so that the general characteristics of the ink are more suitable for jet printing, and meanwhile, the refractive indexes of the two diluting monomers are higher, so that the light transmittance of the ink can be improved in a specific proportion.

Preferably, the silicone-modified polyester acrylate oligomer contains 1 to 3, such as 1, 2 or 3, preferably 2 acrylate functional groups.

In the invention, the number of acrylate functional groups contained in the organic silicon modified polyester acrylate oligomer is limited to 1-3, the more the number of the functional groups is, the stronger the photoreaction activity is, but the more the number of the relative functional groups is, the higher the chemical bond shrinkage is while the reactivity is enhanced, the larger the film shrinkage rate is, and the film adhesion is deteriorated and the physical and mechanical properties are reduced due to the increased shrinkage rate. The organic silicon modified polyester acrylate oligomer with specific acrylate functional group number can improve the light transmittance and the photocuring rate of the ink.

Preferably, the surface tension of the organic silicon modified polyester acrylate oligomer is 5-45mN/m, preferably 20-35 mN/m; the viscosity is from 30 to 500 mPas, preferably from 70 to 150 mPas.

Wherein the surface tension may be: 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35 and 35mN/m, and the viscosity may be 70, 80, 90, 100, 110, 120, 130, 140, 150 mPas, but the above-mentioned ranges are not limited thereto, and other values not recited are also applicable.

The film packaging jet printing ink requires that the surface tension of the ink is 30-50mN/m at normal temperature and normal pressure, the viscosity is 9-25cp, the jet printing effect of the ink in the state range is good, and the integral jet printing effect of the ink can reach the best by limiting the surface tension and the viscosity of the organic silicon modified polyester acrylate.

Preferably, the aliphatic urethane acrylate oligomer contains 2 to 6, such as 2, 3, 4, 5 or 6, preferably 2 acrylate functions. The elongation is 100-.

Wherein the elongation may be: 300%, 350%, 400%, 450%, 500%, 550%, 600%, 650%, 700%, 750%, 800%, 850%, but not limited to the above recited values, other unrecited values within the above numerical range are equally applicable.

Preferably, the diluent monomer comprises one or more of monofunctional, difunctional and multifunctional, and comprises long-chain aliphatic or acrylate and/or methacrylate containing benzene ring substitution.

Preferably, the diluent monomer comprises any one or more of methyl acrylate, butyl acrylate, ethyl acrylate, n-butyl acrylate, octadecyl acrylate, alkoxy dodecyl acrylate, 2-phenoxyethyl methacrylate, 1, 12-dodecanediol diacrylate, 1, 6 hexanediol diacrylate, ethoxylated nonylphenol acrylate, and the like. Preferably 1.6 hexanediol diacrylate or 2-phenoxyethyl methacrylate.

Preferably, the photoinitiator includes any one or a combination of at least two of a benzoin photoinitiator, an alkyl benzophenone photoinitiator, an acyl phosphorus oxide photoinitiator or an anthrone photoinitiator, such as a combination of a benzoin photoinitiator and an alkyl benzophenone photoinitiator, a combination of an alkyl benzophenone photoinitiator and an acyl phosphorus oxide photoinitiator, or a combination of an acyl phosphorus oxide photoinitiator and an anthrone photoinitiator, and the like, but not limited to the above-listed combinations, and other combinations not listed within the above-mentioned combinations are also applicable.

Preferably, the auxiliary agent comprises any one of or a combination of at least two of a leveling agent, a defoaming agent or a film-forming auxiliary agent.

The amount of the auxiliary agent may be 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts, and the auxiliary agent may be a combination of a leveling agent and an antifoaming agent, a combination of an antifoaming agent and a film-forming auxiliary agent, or a combination of a leveling agent and a film-forming auxiliary agent, but is not limited to the above-mentioned values or combinations, and other values or combinations not listed in the above-mentioned values or combinations are also applicable.

Compared with the prior art, the UV ink-jet printing ink has the beneficial effects that: through the compounding and synergistic effect of the organic silicon modified polyester acrylate oligomer, the aliphatic polyurethane acrylate oligomer and the diluent monomer, the characteristics of high flexibility, high light transmittance, high photocuring rate and the like of the UV ink-jet printing ink are obviously improved. Meanwhile, the color is low, the smell is low, the leveling property is good, the volatility is low, and the yellowing resistance is realized; by selecting the organic silicon modified polyester acrylate oligomer with specific acrylate functional group number, the aliphatic polyurethane acrylate oligomer and the diluent monomer, the flexibility, the light transmittance and the light curing rate of the UV ink-jet printing ink are improved.

[ detailed description ] embodiments

Example (b):

in order to verify the effectiveness of the present solution, this example provides 9 examples and 10 comparative examples, the formulation and components of which are shown in table 1, and the formulation in table 1 is in parts by weight.

TABLE 1 composition ratio table of examples 1-10 and comparative examples 1-8

Wherein:

the organic silicon modified polyester acrylate oligomer A1 is purchased from Xinyue, has the model number of KR-5230 and the number of acrylate functional groups of 1;

the organic silicon modified polyester acrylate oligomer A2 is purchased from Boxing, the model is B-808, and the number of acrylate functional groups is 3;

the aliphatic polyurethane acrylate oligomer B1 is purchased from Sartomer with the model number of CN8888 and the number of acrylate functional groups of 2;

the diluent monomer C1 is 2-phenoxyethyl methacrylate, and the diluent monomer C2 is 1.6 hexanediol diacrylate;

photoinitiator D was obtained from Basff as irgacure 754;

leveling agent E was purchased from Pickering chemical Co., Ltd, and was model BYK-066N.

The preparation method of the jet printing ink in each of the above embodiments is as follows: the organosilicon modified polyester acrylate oligomer, the aliphatic polyurethane acrylate oligomer, the diluent monomer, the photoinitiator and the auxiliary agent were stirred for 2.5 hours at 1000rpm with a disperser according to the formulation of examples 1 to 9, and then filtered with a1 μm filter to obtain the UV ink-jet printing ink.

In other embodiments, the stirring rate is 600-1500rpm for 2-3h, wherein the stirring rate can be 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, etc., and the stirring time can be 2h, 2.5h, 3h, etc., but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.

Testing the coating film characteristics:

the inks for UV inkjet printing provided in examples 1 to 9 and comparative examples 1 to 10 were injected into ink capsules of a Kateeva inkjet printer, respectively, and the resulting ink coatings were subjected to a film property test and a reliability test using an LED lamp of 395nm, an exposure lamp power set to 400mJ/cm2, a head temperature set to 45 ℃, inkjet on a test substrate (glass having alumina deposited on the surface) using a jet printing mode program.

1. Yellowing resistance test

Putting the sample into a yellowing resistance test box, receiving light source irradiation for 24h at a constant temperature of 50 ℃, putting the sample into a standard light source box after the sample is cooled, adopting a D65 light source, visually observing the difference between the test sample and an original sample which is not tested, and grading by using a GB/T250 color-changing card.

The standard for the yellowing resistance test is as follows:

o: the tested sample has no difference with the original sample which is not tested, and the transparency is not reduced;

x: the difference between the test sample and the original sample which is not tested is large, the test sample is yellowed, and the transparency is obviously reduced.

2. Adhesion test

And (3) carrying out adhesion test on the sample by a check method, cutting the ink coating to the surface of the substrate to form a check scratch, sticking and tearing by using a 3M adhesive tape, and observing the falling condition of the coating.

The adhesion test criteria are as follows:

o: no drop trace exists;

and (delta): the falling rate is within 5 percent, and the corner falls slightly but does not fall into pieces;

x: the falling rate is more than 5 percent, and a large area of the film falls off.

3. And (3) testing the bending property:

the sample plate was bent 180 degrees and 50 times, and was wound around a diameter of 1 mm, and then the surface condition of the coating film was observed.

The bending test criteria are as follows:

o: the surface of the coating film has no obvious crease, and the flexibility is good;

x: the film surface has 1 or more folds and poor flexibility.

4. Edge linearity test

The sample was placed on a sample holder using an electron microscope of type xipek TXD200V and the surface morphology of the sample was visually observed.

The evaluation criteria for the edge linearity test are as follows:

o: the edge linearity of the ink-jet printing pattern is good;

x: the edge linearity of the inkjet printed pattern is poor.

5. Surface flatness test

The sample was placed on a sample holder using an electron microscope of type xipek TXD200V and the surface morphology of the sample was visually observed.

The surface flatness test evaluation criteria are as follows:

o: the surface of the coating film is flat and smooth, and has no obvious concave-convex defect;

x: the surface of the coating film is rough and has obvious concave-convex defects.

6. Volatility test

And (3) carrying out temperature programming on the sample from 25 ℃ to 150 ℃, wherein the temperature raising rate is5 ℃/min, and measuring the mass change condition of the ink coating before and after.

The evaluation criteria for the volatility test were as follows:

o: the quality of the coating film has no obvious change, and no obvious volatile substance is separated out;

x: the quality of the coating film is obviously changed, and obvious volatile substances are separated out.

7. Double 85 test

The samples were placed at a temperature of 85 ℃ and a humidity of 85% RH to test their degree of aging resistance and insulating properties.

The double 85 test criteria are as follows:

o: the insulating property of the coating film is not reduced, and the ageing resistance is good;

x: the insulating property of the coating film is reduced, and the ageing resistance is poor.

8. High and low temperature cycle test

Through high-low temperature cold-hot circulation, the temperature range of a sample is controlled to be-20-150 ℃, the humidity range is controlled to be 20-98% RH, the cooling rate is 1 ℃/min, the heating rate is 2 ℃/min, and after continuous testing for 48h, the surface condition of an ink coating is visually observed under an electron microscope with the model of Sipek TXD200V at 25 ℃.

The evaluation criteria of the high-low temperature cycle test are as follows:

o: the surface of the coating film has no obvious cracks and other defects;

x: the surface of the coating film has obvious cracks and other defects.

9. And (3) testing the photocuring rate:

the absorption peak intensities of the photocurable composition were measured at about 1635cm-1(C ═ C) and 1720cm-1(C ═ O) using FT-IR (Nicolet iS5, Thermo). First, the photocurable composition was jet-printed on an activated glass substrate using a Kateeva jet printer and a film sample having a thickness of 3 μm was prepared after 10S irradiation by UV at 100mW/cm 2. The cured film was cut into a sample, and this was used to measure absorption peak intensities at 1635cm-1(C ═ C) and 1720cm-1(C ═ O) using FT-IR (nicoietis 5, Thermo).

The formula of light-curing rate (%) was calculated as |1- (X/Y) | 100%, (X is the ratio of the absorption peak intensity of the cured film in the vicinity of 1635cm-1 to the absorption peak intensity in the vicinity of 1720cm-1, and Y is the ratio of the absorption peak intensity of the light-curing composition in the vicinity of 1635cm-1 to the absorption peak intensity in the vicinity of 1720 cm-1)

10. And (3) testing light transmittance:

using an ultraviolet visible spectrophotometer UV754N, shanghai instrument electrical analyzer). The photocurable composition was spray printed on the activated glass substrate using a Kateeva spray printer and irradiated by UV at 200mW/cm2 to prepare a film sample having a thickness of 5 μm, and the light transmittance of the cured film was measured in the visible light range of 550nm using an ultraviolet-visible spectrophotometer UV754N, shanghai instrument electric analyzer).

The test results of examples 1 to 9 and comparative examples 1 to 10 are shown in Table 2.

TABLE 2 test results of examples 1-9 and comparative examples 1-10

The results in table 2 show that the ink for UV inkjet printing provided by the present invention has the characteristics of high flexibility, high light transmittance, high light curing rate, etc. Compared with the comparative examples 1-8 and 4-9, the organic silicon polyester acrylate oligomer with specific acrylate functional groups, the aliphatic polyurethane acrylate oligomer and the diluent monomer are compounded and have synergistic effect, so that the flexibility, the light transmittance and the light curing rate of the UV ink-jet printing ink are improved; comparing examples 1, 3, and 8, and comparative examples 1 to 3, it can be found that the flexibility, light transmittance, and photo-curing rate of the UV inkjet printing ink are further improved in the preferable raw material range of the present invention, and comparative example 9 can be found that the diluent monomer may be one or more.

What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.