Photosensitive copolymer, ink composition and preparation method and application thereof

Abstract

The application discloses a photosensitive copolymer, an ink composition and a preparation method and application thereof, relates to the technical field of PCB imaging ink, and comprises the following components: a bio-based structure photosensitive copolymer, a polyurethane acrylate prepolymer, a photoinitiator and an auxiliary agent. The structural formula of the bio-based structure photosensitive copolymer is as follows: wherein x, y, z, o and p are greater than 0. The imaging ink composition uses the bio-based structure photosensitive copolymer as a base film-forming resin, has the characteristics of green environmental protection, reduces the dependence of the ink composition on petroleum-based raw materials, and in addition, the bio-based structure photosensitive copolymer makes the ink composition excellent in performance, has good performances in terms of adhesion, hardness, resolution and plating resistance, and has wide application space and market prospects.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of PCB imaging ink, in particular to a photosensitive copolymer, an ink composition, and a preparation method and application thereof. BACKGROUND

[0002] Photoresist, also known as photoresist, is a photosensitive material whose solubility, adhesion, and other properties change under light or irradiation. After exposure, development, etching, and other steps, the pattern on the mask can be transferred to the substrate. Photoresist is a key electronic product in microfabrication technology and can be widely used in the processing and manufacturing of semiconductors, liquid crystal displays, and printed circuit boards (PCB). Photoresist can be divided into positive photoresist and negative photoresist according to the removal and retention of the exposed area during development. Positive photoresist has increased solubility after exposure, while negative photoresist has decreased solubility after exposure.

[0003] Imaging ink is mainly composed of film-forming resin, active dilution, photoinitiator, pigment, filler, solvent, etc. Film-forming resin, as the main component, is the carrier of other components and can be dissolved in the developer, directly determining the resolution, heat resistance, and mechanical properties of the photoresist. The main film-forming resin of photoresist usually comes from the modification or deep processing of petrochemical raw materials, which puts a burden on non-renewable petrochemical resources and may cause harm to the natural environment and human health. Secondly, although photoresist has certain removal and retention properties during development, there are still challenges in terms of resolution, heat resistance, and mechanical properties in practical applications.

[0004] In this context, bio-based materials have become a field of interest. Bio-based materials are produced using plant raw materials, including grains, beans, trees, straw, and other plants and their residues and contents, and have the characteristics of green, environmental friendliness, and resource conservation, making them one of the key areas of future global development. Therefore, bio-based materials are expected to become a sustainable alternative to photoresist and other fields, providing new solutions to the challenges currently faced by technology. SUMMARY

[0005] The first technical problem to be solved by the present application is:

[0006] To provide an ink composition.

[0007] The second technical problem to be solved by the present application is:

[0008] To provide a preparation method of the ink composition.

[0009] The third technical problem to be solved by the present application is:

[0010] The application of the ink composition.

[0011] The application further provides an ink, which comprises the ink composition.

[0012] To solve the first technical problem, the application adopts the technical scheme of:

[0013] An ink composition, raw materials of the ink composition comprising the following components:

[0014] A bio-based structural photosensitive copolymer;

[0015] A polyurethane acrylate prepolymer;

[0016] A photoinitiator;

[0017] An auxiliary agent;

[0018] The structural formula of the bio-based structural photosensitive copolymer is as follows:

[0019]

[0020] Wherein, x, y, z, o and p > 0.

[0021] According to an embodiment of the application, one of the technical schemes has at least one of the following advantages or beneficial effects:

[0022] The imaging ink composition of the application uses a bio-based structural photosensitive copolymer as a base film-forming resin, which has the characteristics of green environmental protection, reduces the dependence of the ink composition on petroleum-based raw materials, and in addition, the presence of the bio-based structural photosensitive copolymer makes the ink composition of the application have excellent performance, and has good performance in terms of adhesion, hardness, resolution and plating resistance, etc., and has broad application space and market prospects.

[0023] Specifically, the bio-based structural photosensitive copolymer of the application is a cardanol structural photosensitive copolymer. In terms of structure, the cardanol structure has a benzene ring, which provides certain mechanical properties and high-temperature resistance; the cardanol structure also has a long aliphatic chain, which can provide good flexibility to the system; the acrylate double bond structure in the bio-based structural photosensitive copolymer has high light reactivity, and participates in the photopolymerization reaction together with the polyurethane acrylate prepolymer to form a bio-based structural-urethane structure crosslinking network, which provides the main properties of the cured product; although the meta-unsaturated double bond contained in the molecular side chain has low reactivity, part of it can still participate in the crosslinking reaction, and cooperates with the acrylate double bond crosslinking network in the bio-based structural photosensitive copolymer to further improve the physical and chemical properties of the cured product.

[0024] According to an embodiment of the application, the raw materials of the ink composition comprise the following components by weight:

[0025] biobased structured photosensitive copolymer, 30-70 parts;

[0026] polyurethane acrylate prepolymer, 15-40 parts;

[0027] photoinitiator, 2-8 parts;

[0028] auxiliary agent, 7-33.

[0029] According to an embodiment of the present application, the method for preparing the biobased structured photosensitive copolymer comprises the following steps:

[0030] S1 mixing propylene glycol methyl ether, acrylic acid, butyl acrylate, styrene, chain transfer agent, initiator under heating condition to obtain a mixture;

[0031] S2 heating and reacting the mixture obtained in step S1 to obtain an acrylate copolymer;

[0032] S3 adding a catalyst, cardanol glycidyl ether, and glycidyl methacrylate mixture to the acrylate copolymer, and heating to react to obtain the biobased structured photosensitive copolymer.

[0033] According to an embodiment of the present application, in step S1, a pretreatment step is further included, in which acrylic acid, butyl acrylate, and styrene are respectively reacted with a polymerization inhibitor p-hydroxyanisole to purify the acrylic acid, butyl acrylate, and styrene.

[0034] According to an embodiment of the present application, the pretreatment comprises the following steps: adding 2000 ppm of the polymerization inhibitor p-hydroxyanisole to the acrylic acid, and distilling under reduced pressure at -0.15 to -0.1 MPa and 70-80°C to obtain purified acrylic acid; adding 2000 ppm of the polymerization inhibitor p-hydroxyanisole to the butyl acrylate, and distilling under reduced pressure at -0.15 to -0.1 MPa and 80-90°C to obtain purified butyl acrylate; and adding 2000 ppm of the polymerization inhibitor p-hydroxyanisole to the styrene, and distilling under reduced pressure at -0.15 to -0.1 MPa and 80-90°C to obtain purified styrene.

[0035] According to an embodiment of the present application, in step S1, the transfer agent comprises mercaptoethanol.

[0036] According to an embodiment of the present application, in step S1, the initiator comprises azobisisobutyronitrile.

[0037] According to an embodiment of the present application, the ratio of the heating temperature in step S1 to the heating temperature in step S2 is 90-95°C: 110-120°C.

[0038] According to an embodiment of the present application, the temperature of the heating in step S1 is not more than 100℃. In the method for preparing the bio-based structural photosensitive copolymer of the present application, the polymerization stage is mild, the main reaction temperature is not more than 100℃, and the copolymer structure has a large adjustable space.

[0039] According to an embodiment of the present application, the catalyst in step S3 comprises triphenylphosphine.

[0040] According to an embodiment of the present application, the method for preparing the bio-based structural photosensitive copolymer comprises the following steps:

[0041] S1 mixing 100-200 parts of propylene glycol methyl ether, 40-55 parts of acrylic acid, 10-30 parts of butyl acrylate, 20-45 parts of styrene, 0.1-1 part of a chain transfer agent, and 0.1-2.5 parts of an initiator under heating conditions to obtain a mixture;

[0042] S2 reacting the mixture obtained in step S1 to obtain an acrylate copolymer;

[0043] S3 adding 0.5-3 parts of a catalyst, 30-170 parts of cardanol glycidyl ether, and 15-50 parts of glycidyl methacrylate to the acrylate copolymer, and reacting under heating to obtain the bio-based structural photosensitive copolymer.

[0044] In the photosensitive grafting stage in step S3, the bio-based cardanol structural compound (cardanol glycidyl ether) is added in a large amount, and the photosensitive grafting process is mild and controllable, so that the product has a high bio-based content, and finally the ink composition has excellent performance.

[0045] According to an embodiment of the present application, the method for preparing the bio-based structural photosensitive copolymer comprises the following steps:

[0046] S1 purifying acrylic acid, butyl acrylate, and styrene;

[0047] S2 adding 30-70 parts of propylene glycol methyl ether in a reaction container, starting stirring, and heating to 90-95℃, and then adding 70-130 parts of propylene glycol methyl ether, 40-55 parts of acrylic acid, 10-30 parts of butyl acrylate, 20-45 parts of styrene, 0.1-1 part of a chain transfer agent, and 0.1-2.5 parts of an initiator to the reaction container, and reacting for 5-6h to obtain a mixture;

[0048] S3 heating the mixture obtained in step S1 to 110-120℃, and continuing to react for 1-1.5h to obtain an acrylate copolymer;

[0049] S4 adding 0.5-3 parts of catalyst, 30-170 parts of cardanol glycidyl ether and 15-50 parts of glycidyl methacrylate mixture into the acrylic ester copolymer, and reacting at 115-120℃ for 6-8h, and then cooling down to obtain the bio-based structured photosensitive copolymer.

[0050] According to an embodiment of the present application, the preparation method of the bio-based structured photosensitive copolymer comprises the following steps:

[0051] S1 purifying acrylic acid, butyl acrylate and styrene;

[0052] S2 adding 30-70 parts of propylene glycol methyl ether into a reaction container, and stirring and heating to 90-95℃, and then adding 70-130 parts of propylene glycol methyl ether, 40-55 parts of acrylic acid, 10-30 parts of butyl acrylate, 20-45 parts of styrene, 0.1-1 part of chain transfer agent and 0.1-2.5 parts of initiator dropwise into the reaction container, and controlling the dropwise adding time to be 3-4h; after the dropwise adding is completed, adding 0.01-0.2 parts of azobisisobutyronitrile as initiator every 1h, and the total reaction time from the end of the dropwise adding to the end of the reaction is 5-6h to obtain a mixture;

[0053] S3 heating the mixture obtained in step S1 to 110-120℃, and continuing to react for 1-1.5h to obtain an acrylic ester copolymer;

[0054] S4 adding 0.5-3 parts of catalyst, 30-170 parts of cardanol glycidyl ether and 15-50 parts of glycidyl methacrylate mixture dropwise into the acrylic ester copolymer, and controlling the dropwise adding time to be 1-2h, and then reacting at 115-120℃ for 6-8h after the dropwise adding is completed, and then cooling down, and adding 0-100 parts of propylene glycol methyl ether to obtain the bio-based structured photosensitive copolymer.

[0055] The 0-100 parts of propylene glycol methyl ether added in step S4 is used to adjust the solid content of the product.

[0056] According to an embodiment of the present application, the polyurethane acrylate prepolymer comprises at least one of Changxing 6113, 6121F-80, 6148J-75, 6148J-75NT, 6150-100 and 61329.

[0057] According to an embodiment of the present application, the photoinitiator comprises at least one of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzophenone, isopropyl thioxanthone and 4-(N,N-dimethylamino)ethyl benzoate.

[0058] According to an embodiment of the present application, the auxiliary agent comprises at least one of active diluent, pigment, antioxidant, polymerization inhibitor, leveling agent and defoaming agent.

[0059] According to an embodiment of the present application, the active diluent comprises at least one of tetrahydrofurfuryl acrylate, tripropyleneglycol diacrylate, dipropyleneglycol diacrylate, 1,6-hexanediol diacrylate, propoxylated neopentylglycol diacrylate, trimethylolpropane triacrylate.

[0060] According to an embodiment of the present application, the pigment comprises at least one of phthalocyanine blue, titanium white, benzidine yellow, phthalocyanine green, permanent red.

[0061] According to an embodiment of the present application, the antioxidant comprises at least one of 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, tert-butyl-4-hydroxyanisole, propyl gallate, tris(2,4-di-tert-butylphenyl) phosphite.

[0062] According to an embodiment of the present application, the polymerization inhibitor comprises at least one of p-hydroxyanisole, hydroquinone, p-benzoquinone, methylhydroquinone, 2-tert-butylhydroquinone.

[0063] According to an embodiment of the present application, the leveling agent comprises at least one of BYK 310, 333, uv3510, uv3570, uv3500, uv3576.

[0064] According to an embodiment of the present application, the defoaming agent comprises at least one of BYK 051, 057, 1610, 1650, 1723, 1781.

[0065] To solve the second technical problem, the present application adopts the technical solution of:

[0066] A method for preparing the ink composition, comprising the following steps:

[0067] A1 mixing bio-based structural photosensitive copolymer, polyurethane acrylate prepolymer and auxiliary agent in a reaction vessel, heating and stirring to obtain a mixture;

[0068] A2 reducing the temperature in the reaction vessel, and adding a photoinitiator to the mixture to obtain the ink composition.

[0069] According to an embodiment of the present application, in the method for preparing the ink composition, the heating temperature in step A1 is 50-60℃.

[0070] According to one embodiment of the present application, in the method for preparing the ink composition, the stirring speed in step A1 is 3000-3200 r / min, and the stirring time is 30-40 min.

[0071] According to one embodiment of the present application, in the method for preparing the ink composition, in step A2, the temperature of the reaction vessel after being lowered is 30-35℃.

[0072] According to one embodiment of the present application, in the method for preparing the ink composition, in step A2, the obtained ink composition is further ground in a grinder, the grinding pressure is 3-5 MPa, the grinding time is 10-20 min, and the ground product is introduced into a packaging container through a high-pressure filtration device, and is stored in a dark, ventilated and low-temperature environment.

[0073] Other features and advantages of the present application will be set forth in the description that follows, and in part will become apparent to those skilled in the art upon examination of the following or can be learned by practice of the present application. DETAILED DESCRIPTION

[0074] In the description of the present application, if first, second, etc. are described, it is only for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features or the sequence of indicated technical features.

[0075] The words "preferably", "more preferably" and the like in the present application refer to embodiments of the present application which can provide certain advantages in certain situations. However, other embodiments can also be preferred in the same or other situations. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not useful, nor does it imply that other embodiments are excluded from the scope of the present application.

[0076] When a numerical range is disclosed herein, the above range is considered to be continuous, and includes the minimum value and the maximum value of the range, and every value between the minimum value and the maximum value. Further, when the range refers to an integer, every integer between the minimum value and the maximum value of the range is included. In addition, when multiple ranges are provided to describe a feature or a characteristic, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein.

[0077] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of the present application.

[0078] The reagents, methods and apparatus employed in the present application are those conventional in the art, unless otherwise specified.

[0079] Example 1

[0080] An ink composition, raw materials of the ink composition are the following components in parts by weight:

[0081] Bio-based structured photosensitive copolymer, 40 parts;

[0082] Polyurethane acrylate prepolymer, 33 parts;

[0083] Active diluent, 15 parts;

[0084] Photoinitiator, 4.4 parts;

[0085] Pigment, 6.4 parts;

[0086] Antioxidant, 0.08 parts;

[0087] Polymerization inhibitor, 0.02 parts;

[0088] Leveling agent, 0.3 parts;

[0089] Defoaming agent, 0.8 parts.

[0090] The polyurethane acrylate prepolymer is Changxing 6113;

[0091] The active diluent is tripropylene glycol diacrylate;

[0092] The photoinitiator is isopropyl thioxanthone and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-propanone;

[0093] The pigment is phthalocyanine blue;

[0094] The antioxidant is tris(2,4-di-tert-butylphenyl) phosphite;

[0095] The polymerization inhibitor is p-hydroxyanisole;

[0096] The leveling agent is BYK310;

[0097] The defoaming agent is BYK051;

[0098] The preparation method of the bio-based structured photosensitive copolymer comprises the following steps:

[0099] S1 add 2000ppm inhibitor p-hydroxyanisole in acrylic acid, and distill under reduced pressure at-0.1MPa, 70℃ to obtain purified acrylic acid; add 2000ppm inhibitor p-hydroxyanisole in butyl acrylate, and distill under reduced pressure at-0.1MPa, 80℃ to obtain purified butyl acrylate; add 2000ppm inhibitor p-hydroxyanisole in styrene, and distill under reduced pressure at-0.1MPa, 80℃ to obtain purified styrene;

[0100] S2 in a reaction vessel, add 62 parts of propylene glycol methyl ether, start stirring, and heat to 90℃, then add 126 parts of propylene glycol methyl ether, 50 parts of purified acrylic acid, 25 parts of purified butyl acrylate, 25 parts of purified styrene, 0.7 parts of chain transfer agent mercaptoethanol, and 0.9 parts of initiator azobisisobutyronitrile dropwise, and the dropwise time is controlled for 4h; after the dropwise addition is completed, 0.09 parts of initiator azobisisobutyronitrile and other raw materials in step S2 are added every 1h to adjust the solid content, and the total holding time from the end of dropwise addition to the end of reaction is 6h, to obtain a mixture;

[0101] S3 after the reaction is completed, heat the mixture obtained in step S1 to 110℃, and continue to react for 1h to obtain an acrylate copolymer;

[0102] S4 add 2 parts of catalyst triphenylphosphine to the acrylate copolymer, and add 50 parts of cardanol glycidyl ether and 47 parts of glycidyl methacrylate mixture dropwise, and the dropwise time is 1h; after the dropwise addition is completed, heat at 115℃ for 7h, and cool to obtain a bio-based structure photosensitive copolymer; test results show that the number average molecular weight is 27600, the molecular weight distribution is 2.43, and the acid value is 120mgKOH / g.

[0103] The preparation method of the above-mentioned ink composition comprises the following steps:

[0104] A1 add 40 parts of bio-based structure photosensitive copolymer, 33 parts of polyurethane acrylate prepolymer 6113, 15 parts of reactive diluent tripropylene glycol diacrylate, 6.4 parts of pigment phthalocyanine blue, 0.08 parts of antioxidant tris(2,4-di-tert-butylphenyl) phosphite, 0.02 parts of inhibitor p-hydroxyanisole, 0.3 parts of leveling agent BYK310, and 0.8 parts of defoaming agent BYK051 into a dispersion vessel, start high-speed mechanical stirring, control the rotating speed to be 3000r / min, heat to 50℃, and stir for 30min to obtain a mixture;

[0105] A2 reduce the temperature to 30℃, add 1.4 parts of photoinitiator isopropyl thioxanthone and 3 parts of photoinitiator 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, and continue to stir for 30min;

[0106] A3 grinds the product obtained in step A2 on a grinder, the grinding pressure is 3 MPa, and the grinding time is 10 min, to obtain the ink composition.

[0107] Example 2

[0108] An ink composition, raw materials of the ink composition are the following components in parts by weight:

[0109] a bio-based structured photosensitive copolymer, 50 parts;

[0110] a polyurethane acrylate prepolymer, 25 parts;

[0111] a reactive diluent, 14 parts;

[0112] a photoinitiator, 5.5 parts;

[0113] a pigment, 4.4 parts;

[0114] an antioxidant, 0.07 parts;

[0115] a polymerization inhibitor, 0.03 parts;

[0116] a leveling agent, 0.5 parts;

[0117] a defoaming agent, 0.5 parts.

[0118] The polyurethane acrylate prepolymer is Changxing 6148J-75;

[0119] The reactive diluent is dipropylene glycol diacrylate;

[0120] The photoinitiator is benzophenone and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide;

[0121] The pigment is benzidine yellow;

[0122] The antioxidant is 2,6-di-tert-butyl-p-cresol;

[0123] The polymerization inhibitor is hydroquinone;

[0124] The leveling agent is BYK uv3510;

[0125] The defoaming agent is BYK1610;

[0126] A preparation method of the bio-based structured photosensitive copolymer, comprising the following steps:

[0127] S1 add 2000 ppm of the polymerization inhibitor p-hydroxyanisole to the acrylic acid and distill under reduced pressure at -0.1 MPa and 70°C to obtain purified acrylic acid; add 2000 ppm of the polymerization inhibitor p-hydroxyanisole to the butyl acrylate and distill under reduced pressure at -0.1 MPa and 80°C to obtain purified butyl acrylate; add 2000 ppm of the polymerization inhibitor p-hydroxyanisole to the styrene and distill under reduced pressure at -0.1 MPa and 80°C to obtain purified styrene;

[0128] S2 in a reaction vessel, add 51 parts of propylene glycol methyl ether, start stirring, and heat to 90°C; add dropwise a mixture of 102 parts of propylene glycol methyl ether, 47 parts of purified acrylic acid, 20 parts of purified butyl acrylate, 33 parts of purified styrene, 0.9 parts of chain transfer agent mercaptoethanol, and 1.2 parts of initiator azobisisobutyronitrile, and control the dropwise addition time to be 3 h; after the dropwise addition is completed, add 0.12 parts of initiator azobisisobutyronitrile every 1 h, and the total holding time from the end of the dropwise addition to the end of the reaction is 6 h, to obtain a mixture;

[0129] S3 after the reaction is completed, heat the mixture obtained in step S1 to 110°C and continue to react for 1 h to obtain an acrylate copolymer;

[0130] S4 add 1.5 parts of catalyst triphenylphosphine to the acrylate copolymer, and add dropwise a mixture of 100 parts of cardanol glycidyl ether and 34 parts of glycidyl methacrylate, with a dropwise addition time of 2 h; after the dropwise addition is completed, heat at 115°C for 8 h, cool, and add 38 parts of propylene glycol methyl ether to obtain a bio-based structural photosensitive copolymer; testing shows that the number average molecular weight of the bio-based structural photosensitive copolymer is 25400, the molecular weight distribution is 2.32, and the acid value is 96 mgKOH / g.

[0131] The preparation method of the above-mentioned ink composition comprises the following steps:

[0132] A1 add 50 parts of bio-based structural photosensitive copolymer, 25 parts of polyurethane acrylate prepolymer 6148J-75, 14 parts of reactive diluent dipropylene glycol diacrylate, 4.4 parts of pigment benzidine yellow, 0.07 parts of antioxidant 2,6-di-tert-butyl-p-cresol, 0.03 parts of polymerization inhibitor hydroquinone, 0.5 parts of leveling agent BYK uv3510, and 0.5 parts of defoaming agent BYK1610 to a dispersion container, start high-speed mechanical stirring, control the rotating speed to be 3000 r / min, heat to 50°C, and stir for 30 min to obtain a mixture;

[0133] A2 reduce the temperature to 30°C, add 2 parts of photoinitiator benzophenone and 3.5 parts of photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and continue to stir for 30 min;

[0134] A3 grinds the product obtained in step A2 on a grinder, the grinding pressure is 3 MPa, and the grinding time is 10 min, to obtain the ink composition.

[0135] Example 3

[0136] An ink composition, raw materials of the ink composition are the following components in parts by weight:

[0137] a bio-based structured photosensitive copolymer, 53 parts;

[0138] a polyurethane acrylate prepolymer, 26 parts;

[0139] a reactive diluent, 9 parts;

[0140] a photoinitiator, 5.5 parts;

[0141] a pigment, 5.1 parts;

[0142] an antioxidant, 0.05 parts;

[0143] a polymerization inhibitor, 0.05 parts;

[0144] a leveling agent, 0.8 parts;

[0145] a defoaming agent, 0.5 parts.

[0146] The polyurethane acrylate prepolymer is Changxing 6121F-80;

[0147] The reactive diluent is trimethylolpropane triacrylate;

[0148] The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanone;

[0149] The pigment is titanium white;

[0150] The antioxidant is tert-butyl-4-hydroxyanisole;

[0151] The polymerization inhibitor is 2-tert-butylhydroquinone;

[0152] The leveling agent is BYK uv3500;

[0153] The defoaming agent is BYK057;

[0154] A preparation method of the bio-based structured photosensitive copolymer, comprising the following steps:

[0155] S1 add 2000ppm inhibitor p-hydroxyanisole in acrylic acid, and distill under reduced pressure at -0.1MPa, 70℃ to obtain purified acrylic acid; add 2000ppm inhibitor p-hydroxyanisole in butyl acrylate, and distill under reduced pressure at -0.1MPa, 80℃ to obtain purified butyl acrylate; add 2000ppm inhibitor p-hydroxyanisole in styrene, and distill under reduced pressure at -0.1MPa, 80℃ to obtain purified styrene;

[0156] S2 in a reaction vessel, add 62 parts of propylene glycol methyl ether, start stirring, and heat to 90℃; add 126 parts of propylene glycol methyl ether, 47 parts of purified acrylic acid, 20 parts of purified butyl acrylate, 33 parts of purified styrene, 0.5 parts of chain transfer agent mercaptoethanol, and 1.5 parts of initiator azobisisobutyronitrile mixture dropwise, and the dropwise time is controlled for 3h; after the dropwise addition is completed, add 0.15 parts of initiator azobisisobutyronitrile every 1h, and the total holding time from the end of dropwise addition to the end of reaction is 6h to obtain a mixture;

[0157] S3 after the reaction is completed, heat the mixture obtained in step S1 to 110℃, and continue to react for 1h to obtain an acrylate copolymer;

[0158] S4 add 1.3 parts of catalyst triphenylphosphine to the acrylate copolymer, and add 150 parts of cardanol glycidyl ether and 17 parts of glycidyl methacrylate mixture dropwise, and the dropwise time is 1h; after the dropwise addition is completed, heat at 115℃ for 8h, and cool to obtain a bio-based structure photosensitive copolymer; test results show that the number average molecular weight is 24800, the molecular weight distribution is 2.56, and the acid value is 96.5mgKOH / g.

[0159] The preparation method of the above-mentioned ink composition comprises the following steps:

[0160] A1 add 53 parts of bio-based structure photosensitive copolymer, 26 parts of polyurethane acrylate prepolymer 6121F-80, 9 parts of reactive diluent trimethylolpropane triacrylate, 5.1 parts of pigment titanium dioxide, 0.05 parts of antioxidant tert-butyl-4-hydroxyanisole, 0.05 parts of inhibitor 2-tert-butyl hydroquinone, 0.8 parts of leveling agent BYK uv3500, and 0.5 parts of defoaming agent BYK057 into a dispersion container, start high-speed mechanical stirring, control the rotating speed to be 3000r / min, heat to 50℃, and stir for 30min to obtain a mixture;

[0161] A2 reduce the temperature to 30℃, add 3.5 parts of photoinitiator 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and 2 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and continue to stir for 30min;

[0162] A3 grinds the product obtained in step A2 on a grinder, the grinding pressure is 3 MPa, and the grinding time is 10 min, to obtain the ink composition.

[0163] Example 4

[0164] An ink composition, raw materials of the ink composition are the following components in parts by weight:

[0165] a bio-based structured photosensitive copolymer, 60 parts;

[0166] a polyurethane acrylate prepolymer, 17 parts;

[0167] an active diluent, 12.5 parts;

[0168] a photoinitiator, 6 parts;

[0169] a pigment, 3.5 parts;

[0170] an antioxidant, 0.05 parts;

[0171] a polymerization inhibitor, 0.05 parts;

[0172] a leveling agent, 0.5 parts;

[0173] a defoaming agent, 0.4 parts.

[0174] The polyurethane acrylate prepolymer is Changxing 61329;

[0175] The active diluent is trimethylolpropane triacrylate;

[0176] The photoinitiator is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone and isopropyl thioxanthone;

[0177] The pigment is phthalocyanine blue;

[0178] The antioxidant is 2,6-di-tert-butyl-p-cresol;

[0179] The polymerization inhibitor is p-hydroxyanisole;

[0180] The leveling agent is BYK uv3576;

[0181] The defoaming agent is BYK1781;

[0182] A preparation method of the bio-based structured photosensitive copolymer, comprising the following steps:

[0183] S1 add 2000ppm inhibitor p-hydroxyanisole in acrylic acid, and distill under reduced pressure at -0.1MPa, 70℃ to obtain purified acrylic acid; add 2000ppm inhibitor p-hydroxyanisole in butyl acrylate, and distill under reduced pressure at -0.1MPa, 80℃ to obtain purified butyl acrylate; add 2000ppm inhibitor p-hydroxyanisole in styrene, and distill under reduced pressure at -0.1MPa, 80℃ to obtain purified styrene;

[0184] S2 in a reaction vessel, add 41 parts of propylene glycol methyl ether, start stirring, and heat to 90℃; add 83 parts of propylene glycol methyl ether, 45 parts of purified acrylic acid, 15 parts of purified butyl acrylate, 40 parts of purified styrene, 0.3 parts of chain transfer agent mercaptoethanol, and 1.8 parts of initiator azobisisobutyronitrile mixture dropwise, and the dropwise time is controlled for 3h; after the dropwise addition is completed, add 0.18 parts of initiator azobisisobutyronitrile every 1h, and the total holding time from the end of dropwise addition to the end of reaction is 5h to obtain a mixture;

[0185] S3 after the reaction is completed, heat the mixture obtained in step S1 to 110℃, and continue to react for 1h to obtain an acrylate copolymer;

[0186] S4 add 1 part of catalyst triphenylphosphine to the acrylate copolymer, and add 150 parts of cardanol glycidyl ether and 17 parts of glycidyl methacrylate mixture dropwise, and the dropwise time is 2h; after the dropwise addition is completed, heat at 115℃ for 8h, cool, and add 94 parts of propylene glycol methyl ether to obtain a bio-based structural photosensitive copolymer; test results show that the number average molecular weight of the bio-based structural photosensitive copolymer is 23200, the molecular weight distribution is 2.86, and the acid value is 80.9mgKOH / g.

[0187] The preparation method of the above-mentioned ink composition comprises the following steps:

[0188] A1 add 60 parts of bio-based structural photosensitive copolymer, 17 parts of polyurethane acrylate prepolymer 61329, 12.5 parts of reactive diluent trimethylolpropane triacrylate, 3.5 parts of pigment phthalocyanine blue, 0.05 parts of antioxidant 2,6-di-tert-butyl-p-cresol, 0.05 parts of inhibitor p-hydroxyanisole, 0.5 parts of leveling agent BYK uv3576, and 0.4 parts of defoaming agent BYK1781 into a dispersion container, start high-speed mechanical stirring, control the rotating speed to be 3000r / min, heat to 50℃, and stir for 30min to obtain a mixture;

[0189] A2 reduce the temperature to 30℃, add 4 parts of photoinitiator 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone and 2 parts of photoinitiator isopropyl thioxanthone, and continue to stir for 30min;

[0190] A3 grinds the product obtained in step A2 on a grinder, the grinding pressure is 3 MPa, and the grinding time is 10 min, to obtain the ink composition.

[0191] Example 5

[0192] An ink composition, raw materials of the ink composition are the following components in parts by weight:

[0193] a bio-based structured photosensitive copolymer, 49 parts;

[0194] a polyurethane acrylate prepolymer, 26 parts;

[0195] a reactive diluent, 13.5 parts;

[0196] a photoinitiator, 6.5 parts;

[0197] a pigment, 3.9 parts;

[0198] an antioxidant, 0.08 parts;

[0199] a polymerization inhibitor, 0.02 parts;

[0200] a leveling agent, 0.6 parts;

[0201] a defoaming agent, 0.4 parts.

[0202] The polyurethane acrylate prepolymer is Changxing 6150-100;

[0203] The reactive diluent is trimethylolpropane triacrylate;

[0204] The photoinitiator is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone and benzophenone;

[0205] The pigment is Ever Red;

[0206] The antioxidant is 2,5-di-tert-butylhydroquinone;

[0207] The polymerization inhibitor is hydroquinone;

[0208] The leveling agent is BYK333;

[0209] The defoaming agent is BYK1723;

[0210] A preparation method of the bio-based structured photosensitive copolymer, comprising the following steps:

[0211] S1 add 2000 ppm of the polymerization inhibitor p-hydroxyanisole to the acrylic acid and distill under reduced pressure at -0.1 MPa and 70°C to obtain purified acrylic acid; add 2000 ppm of the polymerization inhibitor p-hydroxyanisole to the butyl acrylate and distill under reduced pressure at -0.1 MPa and 80°C to obtain purified butyl acrylate; add 2000 ppm of the polymerization inhibitor p-hydroxyanisole to the styrene and distill under reduced pressure at -0.1 MPa and 80°C to obtain purified styrene;

[0212] S2 in a reaction vessel, add 62 parts of propylene glycol methyl ether, start stirring, and heat to 90°C; add dropwise a mixture of 126 parts of propylene glycol methyl ether, 50 parts of purified acrylic acid, 25 parts of purified butyl acrylate, 25 parts of purified styrene, 0.3 parts of chain transfer agent mercaptoethanol, and 1.5 parts of initiator azobisisobutyronitrile, and control the dropwise addition time to be 4 h; after the dropwise addition is completed, add 0.15 parts of initiator azobisisobutyronitrile every 1 h, and the total holding time from the end of the dropwise addition to the end of the reaction is 5 h, to obtain a mixture;

[0213] S3 after the reaction is completed, heat the mixture obtained in step S1 to 110°C and continue to react for 1 h to obtain an acrylate copolymer;

[0214] S4 add 2 parts of catalyst triphenylphosphine to the acrylate copolymer, and add dropwise a mixture of 100 parts of cardanol glycidyl ether and 34 parts of glycidyl methacrylate, with a dropwise addition time of 2 h; after the dropwise addition is completed, heat at 115°C for 8 h, and then cool to obtain a bio-based structural photosensitive copolymer; testing shows that the number average molecular weight of the bio-based structural photosensitive copolymer is 24200, the molecular weight distribution is 2.75, and the acid value is 120.3 mgKOH / g.

[0215] The preparation method of the above-mentioned ink composition comprises the following steps:

[0216] A1 add 49 parts of the bio-based structural photosensitive copolymer, 26 parts of polyurethane acrylate prepolymer 6150-100, 13.5 parts of reactive diluent trimethylolpropane triacrylate, 3.9 parts of pigment permanent red, 0.08 parts of antioxidant 2,5-di-tert-butylhydroquinone, 0.02 parts of polymerization inhibitor hydroquinone, 0.6 parts of leveling agent BYK333, and 0.4 parts of defoaming agent BYK1723 to a dispersion container, start high-speed mechanical stirring, control the rotating speed to be 3000 r / min, heat to 50°C, and stir for 30 min to obtain a mixture;

[0217] A2 reduce the temperature to 30°C, add 4 parts of photoinitiator 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone and 2.5 parts of photoinitiator benzophenone, and continue to stir for 30 min;

[0218] A3 grinds the product obtained in step A2 on a grinder, the grinding pressure is 3 MPa, and the grinding time is 10 min, to obtain the ink composition.

[0219] Comparative Example 1

[0220] No polyurethane acrylate prepolymer is added in Comparative Example 1.

[0221] An ink composition, raw materials of the ink composition are the following components in parts by weight:

[0222] Bio-based structured photosensitive copolymer, 66 parts;

[0223] Active diluent, 22 parts;

[0224] Photoinitiator, 5.5 parts;

[0225] Pigment, 5.1 parts;

[0226] Antioxidant, 0.05 parts;

[0227] Polymerization inhibitor, 0.05 parts;

[0228] Leveling agent, 0.8 parts;

[0229] Defoaming agent, 0.5 parts.

[0230] The active diluent is trimethylolpropane triacrylate;

[0231] The photoinitiator is 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanone;

[0232] The pigment is titanium white;

[0233] The antioxidant is tert-butyl-4-hydroxyanisole;

[0234] The polymerization inhibitor is 2-tert-butyl hydroquinone;

[0235] The leveling agent is BYK uv3500;

[0236] The defoaming agent is BYK057;

[0237] The preparation method of the bio-based structured photosensitive copolymer comprises the following steps:

[0238] S1 add 2000ppm inhibitor p-hydroxyanisole in acrylic acid, and distill under reduced pressure at -0.1MPa, 70℃ to obtain purified acrylic acid; add 2000ppm inhibitor p-hydroxyanisole in butyl acrylate, and distill under reduced pressure at -0.1MPa, 80℃ to obtain purified butyl acrylate; add 2000ppm inhibitor p-hydroxyanisole in styrene, and distill under reduced pressure at -0.1MPa, 80℃ to obtain purified styrene;

[0239] S2 in a reaction vessel, add 62 parts of propylene glycol methyl ether, start stirring, and heat to 90℃; add 126 parts of propylene glycol methyl ether, 47 parts of purified acrylic acid, 20 parts of purified butyl acrylate, 33 parts of purified styrene, 0.5 parts of chain transfer agent mercaptoethanol, and 1.5 parts of initiator azobisisobutyronitrile mixture dropwise, and the dropwise time is controlled for 3h; after the dropwise addition is completed, add 0.15 parts of initiator azobisisobutyronitrile every 1h, and the total holding time from the end of dropwise addition to the end of reaction is 6h to obtain a mixture;

[0240] S3 after the reaction is completed, heat the mixture obtained in step S1 to 110℃, and continue to react for 1h to obtain an acrylate copolymer;

[0241] S4 add 1.3 parts of catalyst triphenylphosphine to the acrylate copolymer, and add 150 parts of cardanol glycidyl ether and 17 parts of glycidyl methacrylate mixture dropwise, and the dropwise time is 1h; after the dropwise addition is completed, heat at 115℃ for 8h, and cool to obtain a bio-based structure photosensitive copolymer; test results show that the number average molecular weight of the bio-based structure photosensitive copolymer is 24800, the molecular weight distribution is 2.56, and the acid value is 96.5mgKOH / g.

[0242] The preparation method of the above-mentioned ink composition comprises the following steps:

[0243] A1 add 66 parts of bio-based structure photosensitive copolymer, 22 parts of active diluent trimethylolpropane triacrylate, 5.1 parts of pigment titanium dioxide, 0.05 parts of antioxidant tert-butyl-4-hydroxyanisole, 0.05 parts of inhibitor 2-tert-butyl hydroquinone, 0.8 parts of leveling agent BYK uv3500, and 0.5 parts of defoaming agent BYK057 into a dispersion container, start high-speed mechanical stirring, control the rotating speed to be 3000r / min, heat to 50℃, and stir for 30min to obtain a mixture;

[0244] A2 reduce the temperature to 30℃, add 3.5 parts of photoinitiator 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and 2 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and continue to stir for 30min;

[0245] A3 grinds the product obtained in step A2 on a grinder, the grinding pressure is 3 MPa, and the grinding time is 10 min, to obtain the ink composition.

[0246] Comparative Example 2

[0247] No bio-based structured photosensitive copolymer prepared in the invention is added in Comparative Example 2.

[0248] An ink composition, raw materials of the ink composition include the following components in parts by weight:

[0249] polyurethane acrylate prepolymer, 52 parts;

[0250] active diluent, 36 parts;

[0251] photoinitiator, 5.5 parts;

[0252] pigment, 5.1 parts;

[0253] antioxidant, 0.05 parts;

[0254] polymerization inhibitor, 0.05 parts;

[0255] leveling agent, 0.8 parts;

[0256] defoaming agent, 0.5 parts.

[0257] The above polyurethane acrylate prepolymer is Changxing 6121F-80;

[0258] The above active diluent is trimethylolpropane triacrylate;

[0259] The above photoinitiator is 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanone;

[0260] The above pigment is titanium white;

[0261] The above antioxidant is tert-butyl-4-hydroxyanisole;

[0262] The above polymerization inhibitor is 2-tert-butyl hydroquinone;

[0263] The above leveling agent is BYK uv3500;

[0264] The above defoaming agent is BYK057;

[0265] The above method for preparing the ink composition includes the following steps:

[0266] A1 52 parts of polyurethane acrylate prepolymer 6121F-80, 36 parts of reactive diluent trimethylolpropane triacrylate, 5.1 parts of pigment titanium dioxide, 0.05 parts of antioxidant t-butyl-4-hydroxyanisole, 0.05 parts of polymerization inhibitor 2-t-butyl hydroquinone, 0.8 parts of leveling agent BYK uv3500, 0.5 parts of defoaming agent BYK057 were added into a dispersion container, high-speed mechanical stirring was started, the rotating speed was controlled to be 3000 r / min, the temperature was increased to 50℃, and the stirring time was 30 min to obtain a mixture;

[0267] A2 the temperature was decreased to 30℃, 3.5 parts of photoinitiator 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and 2 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone were added, and the stirring was continued for 30 min;

[0268] A3 the product obtained in step A2 was ground on a grinder, the grinding pressure was 3 MPa, and the grinding time was 10 min to obtain the ink composition.

[0269] Performance test:

[0270] The ink compositions obtained in examples 1-5 and comparative examples 1-2 were screen printed on a PCB substrate which was subjected to acid treatment, sanding, water washing, baking, and dust removal, and then subjected to processes of 80℃ / 20 min pre-baking, 200 mj / cm 2 energy exposure, 30℃ / 1wt%Na2CO3 solution development, acid etching solution etching, 50℃ / 5wt%NaOH solution film removal, etc. The adhesion test was carried out according to ASTM D3359, the hardness test was carried out according to ASTM D3363, and the main performance test results are shown in Table 1.

[0271] Table 1

[0272]

[0273] It can be seen from Table 1 that: compared with the examples, no polyurethane acrylate prepolymer was added in comparative example 1, and a crosslinked network with sufficient density was not formed, so that the hardness of the cured imaging ink decreased, the resolution decreased due to overdevelopment, and the plating resistance also deteriorated; compared with the examples, no bio-based structural photosensitive copolymer prepared in the application was added in comparative example 2, the hardness increased, the adhesion of the cured product deteriorated due to the lack of flexible bio-based molecular chains balancing the brittleness, and the development was insufficient due to the lack of carboxyl structure; the performance of example 3 was the best.

[0274] In summary, the imaging ink composition prepared by taking the bio-based structural copolymer prepared in the application as the main component has good performances in adhesion, hardness, resolution and plating resistance and the like in the PCB process, and has wide application space and market prospect.

[0275] The above is only an embodiment of the application, and does not limit the patent scope of the application, and any equivalent transformation or direct or indirect application in the related technical field by using the content of the application specification is also included in the patent protection scope of the application.

Claims

1. An ink composition characterized in that: The raw materials of the ink composition include the following components by weight: a bio-based structured photosensitive copolymer, 30-70 parts; a polyurethane acrylate prepolymer, 15-40 parts; a photoinitiator, 2-8 parts; an auxiliary agent, 7-33; the bio-based structured photosensitive copolymer has the following structural formula: ； wherein x, y, z, o and p > 0; the bio-based structured photosensitive copolymer is prepared by the following method: S1 under heating conditions, mixing propylene glycol methyl ether, acrylic acid, butyl acrylate, styrene, chain transfer agent mercaptoethanol, initiator azobisisobutyronitrile to obtain a mixture; S2 heating and reacting the mixture obtained in step S1 to obtain an acrylate copolymer; S3 adding a catalyst triphenylphosphine, cashew phenol glycidyl ether, a mixture of glycidyl methacrylate to the acrylate copolymer, and heating to obtain the bio-based structured photosensitive copolymer; the ratio of the heating temperature in step S1 to the heating temperature in step S2 is 90-95℃: 110-120℃.

2. An ink composition according to claim 1, characterised in that: In step S1, a pretreatment step is further included: reacting acrylic acid, butyl acrylate and styrene with a polymerization inhibitor p-hydroxyanisole, respectively, to purify the acrylic acid, butyl acrylate and styrene.

3. The ink composition of claim 1, wherein: The polyurethane acrylate prepolymer includes at least one of Longxing 6113, 6121F-80, 6148J-75, 6148J-75NT, 6150-100, and 61329.

4. The ink composition according to claim 1, characterized in that: The photoinitiator includes at least one of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzophenone, isopropyl thioxanthone, and 4-(N,N-dimethylamino)ethyl benzoate.

5. The ink composition of claim 1, wherein: The auxiliary agent includes at least one of an active diluent, a pigment, an antioxidant, a polymerization inhibitor, a leveling agent, and a defoaming agent.

6. A method of preparing an ink composition as claimed in any one of claims 1 to 5, characterised in that: including the following steps: A1 mixing the bio-based structured photosensitive copolymer, the polyurethane acrylate prepolymer and the auxiliary agent in a reaction vessel, heating and stirring to obtain a mixture; A2 reducing the temperature in the reaction vessel and adding the photoinitiator to the mixture to obtain the ink composition.

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