Thermal acid generator as well as preparation and application thereof

Abstract

The invention provides a thermal acid generator and a preparation method and application thereof.The thermal acid generator has the structure shown in the formula (I), the thermal acid generator can improve the molecular stability, and when the thermal acid generator is used in a thermocuring composition, initiation activity can be kept under the condition that other formula components do not need to be changed, the stability of a product is improved, and the thermal acid generator can be applied to the thermocuring composition. And the curing speed is kept unchanged.

Description

Technical Field

[0001] The present invention belongs to the field of organic chemistry, and particularly relates to a heat acid generator and a preparation method and application thereof. Background Art

[0002] The heat acid generator can be applied to components requiring optical properties such as displays, optical waveguides, and optical lenses, and can also be applied to various uses such as coatings, inks, inkjet inks, anti-etching films, liquid anti-etching agents, negative anti-etching agents, anti-etching agents for MEMS, negative photosensitive materials, various adhesives, molding materials, casting molding materials, putties, glass fiber impregnating agents, packing materials, sealants, encapsulants, optical semiconductor (LED) sealants, optical waveguide materials, nanoimprint materials, materials for stereolithography and microstereolithography, and ACF (anisotropic conductive film).

[0003] It is known that benzylaniline salts can generate acid by heating to cure cationic curable compounds, and N-(4-methoxybenzyl)-N,N-dimethylbenzenonium salt is a commonly used heat acid generator.

[0004] However, in practical applications, the stability problem of the product needs to be further improved. Restricted by the actual molecular structure, the curing speed and stability of the product are relatively fixed. It seems difficult to solve whether the stability of the product can be improved without changing the product structure and formula. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a heat acid generator and a preparation method and application thereof.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] On the one hand, the present invention provides a heat acid generator, and the heat acid generator has a structure shown in formula (I):

[0008]

[0009]

[0010] Wherein, R1 represents deuterium or a straight-chain or branched-chain alkyl group of C1-C 10 ;

[0011] R2 and R3 independently represent hydrogen, deuterium, a straight-chain or branched-chain alkyl group of C1-C 10 or a deuterium-substituted straight-chain or branched-chain alkyl group of C1-C 10 , and at least one of R2 and R3 is deuterium or a deuterium-substituted straight-chain or branched-chain alkyl group of C1-C 10 ;

[0012] B represents a non-nucleophilic anion.

[0013] In the present invention, the inventors unexpectedly found that deuterating the hydrogen on the methyl group of N-(4-methoxybenzyl)-N,N-dimethylbenzenium salt can improve the stability of the molecule and the curing rate remains unchanged.

[0014] In the present invention, the C1-C 10 may be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C 10 .

[0015] Preferably, R1 represents hydrogen, methyl or ethyl.

[0016] Preferably, R2 and R3 are independently selected from hydrogen, deuterium, methyl, deuterated methyl, ethyl or deuterated ethyl, and at least one of R2 and R3 is deuterium, deuterated methyl or deuterated ethyl.

[0017] Preferably, B - preferably C n Q 2n+1 SO3 - , BQ4 - , SbQ6 - , AsQ6 - , PQ6 - or [B(C6Q5)4] - , wherein Q represents hydrogen or halogen, and n is an integer from 1 to 8 (such as 1, 2, 3, 4, 5, 6, 7 or 8).

[0018] Preferably, the halogen is F, Cl, Br or I, preferably F.

[0019] Preferably, the thermal acid generator is selected from any one of the following compounds:

[0020]

[0021]

[0022] In the present invention, the thermal acid generator can be synthesized with reference to the synthesis method in JP2023052255A.

[0023] Preferably, the preparation method of the thermal acid generator as described above includes the following steps:

[0024] (1) The compound of formula II reacts with the compound of formula III to obtain the compound of formula IV, and the reaction formula is as follows:

[0025]

[0026] (2) The compound of formula IV reacts with an acid to obtain the thermal acid generator shown in formula (I), and the reaction formula is as follows:

[0027]

[0028] Wherein X represents a halogen.

[0029] Preferably, the molar ratio of the compound of formula II to the compound of formula III in step (1) is 0.8 - 2:2 - 0.8, such as 0.8:2, 0.8:1.8, 0.8:1.5, 0.8:1.3, 0.8:1.0, 0.8:08, 1:2, 1:1.8, 1:1.5, 1:1.3, 1:0.8, 1.3:0.8, 1.3:2, 1.3:1.5, 1.5:1.3, 1.5:2, 1.5:0.8, 1.8:2, 1.8:1, 1.8:0.8, 2:1.5, 2:1.8, 2:0.8, etc.

[0030] Preferably, the reaction in step (1) is carried out in a solvent selected from any one or a combination of at least two of acetonitrile, dichloromethane, dichloroethane, benzene or toluene.

[0031] Preferably, the temperature of the reaction in step (1) is 20 - 60 °C, such as 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C or 60 °C, and the reaction time is 3 - 8 h, such as 3 h, 4 h, 5 h, 6 h, 7 h or 8 h.

[0032] Preferably, the molar ratio of the compound of formula IV to the acid in step (2) is 0.8 - 2:2:0.8, such as 0.8:2, 0.8:1.8, 0.8:1.5, 0.8:1.3, 0.8:1.0, 0.8:08, 1:2, 1:1.8, 1:1.5, 1:1.3, 1:0.8, 1.3:0.8, 1.3:2, 1.3:1.5, 1.5:1.3, 1.5:2, 1.5:0.8, 1.8:2, 1.8:1, 1.8:0.8, 2:1.5, 2:1.8, 2:0.8, etc.

[0033] Preferably, the acid in step (2) is selected from hexafluorophosphoric acid, hexafluoroantimonic acid, hexafluoroarsenic acid, tetraphenylboric acid, tetrakis(pentafluorophenyl)boric acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, hexafluoroethanesulfonic acid, hexafluorobutanesulfonic acid, nonafluorobutanesulfonic acid or nonafluoropentanesulfonic acid.

[0034] Preferably, the reaction in step (2) is carried out in a solvent which is any one or a combination of at least two of acetone, cyclohexanone or butanone.

[0035] Preferably, the reaction in step (2) is carried out at room temperature, and the reaction time is 0.5 - 2 h, such as 0.5 h, 0.8 h, 1 h, 1.3 h, 1.5 h, 1.8 h or 2 h.

[0036] On the other hand, the present invention provides a thermosetting composition, which comprises the thermoacid generator as described above.

[0037] Preferably, the thermosetting composition comprises the following components by mass:

[0038]

[0039] In the present invention, the content of the thermoacid generator in the thermosetting composition can be 0.1 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.

[0040] In the present invention, the content of the polycarbonate in the thermosetting composition can be 0.1 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight or 20 parts by weight.

[0041] In the present invention, the content of the leveling agent in the thermosetting composition can be 0.01 part by weight, 0.03 part by weight, 0.05 part by weight, 0.08 part by weight, 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight or 0.5 part by weight.

[0042] Preferably, the epoxy resin is selected from bisphenol A, bisphenol F, phenolic epoxy resin, non-aromatic epoxy resin, alicyclic epoxy resin, epoxidized polysulfide and epoxy-functional acrylic resin or any combination thereof.

[0043] Preferably, the leveling agent is selected from polyether-modified polydimethylsiloxane, lauryl (meth)acrylate, polybutyl (meth)acrylate, poly(2-ethylhexyl) (meth)acrylate, or fluorinated polymer or polysiloxane.

[0044] The thermoacid generator shown by the general formula (I) of the present invention is applied to the curing composition. Without changing the existing use formula of the thermoacid generator, it can maintain the initiation activity after application, and improve the stability of the product.

[0045] On the other hand, the present invention provides a cured film, which is obtained by curing the thermosetting composition as described above.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] The thermoacid generator of the present invention can improve the stability of molecules. When it is used in the thermosetting composition, it can maintain the initiation activity without changing other formula components, improve the stability of the product, and keep the curing speed unchanged. Detailed implementation manners

[0048] The technical solution of the present invention will be further described below through specific implementation manners. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0049] Preparation Example

[0050] Example 1

[0051]

[0052] Step (1):

[0053] Add 50.0 g of N-methyl-N-trideuteriomethylaniline (cas: 88889-00-3), 63.0 g of 4-methoxybenzyl chloride and 16.5 g of acetonitrile into a 500 mL four-necked flask, mix and heat to 50 °C, stir for 5 h, track by liquid phase until the reaction raw materials no longer change, then add 250 g of acetone to the reaction solution, cool down to below 10 °C and stir for 1 h, filter and dry to obtain 80.2 g of N-(4-methoxybenzyl)-N-methyl-N-(trideuteriomethyl)aniline chloride.

[0054] Step (2):

[0055] Add 50.0 g of -(4-methoxybenzyl)-N-methyl-N-(trideuteriomethyl)aniline chloride obtained in step 1, 200 g of ionized water and 250 g of dichloromethane into a 500 mL four-necked flask, add 125.0 g of sodium tetrakis(pentafluorophenyl)borate under stirring, stir at room temperature for 1 h until the reaction is complete, then remove the water layer, wash the organic layer 3 times with 300 g of deionized water, and then remove the solvent from the organic layer, and recrystallize with ethyl acetate to obtain 150.3 g of the target product. MS (m / z): 245.

[0056] Example 2

[0057] Referring to the method of Example 1, using deuterated N,N-dialkylaniline, 4-alkylbenzyl chloride and salts of corresponding anions as starting materials, the compounds 2-30 shown in Table 1 were prepared.

[0058] The structures of the target products and their MS (m / z) data are listed in Table 1.

[0059] Table 1

[0060]

[0061]

[0062]

[0063]

[0064] Application Example

[0065] By formulating an exemplary thermosetting composition, the application performance of the thermal initiator represented by formula (I) of the present invention was tested.

[0066] The formulation of the thermosetting composition is as follows:

[0067]

[0068]

[0069] Epoxy resin 6110 is 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate; the thermal acid generator is the deuterated thermal acid generator represented by the general formula (I) of the present invention or a conventional thermal acid generator used for comparison; the PC solution is 1,2-propylene carbonate; BYK307 is a leveling agent polyether-modified polydimethylsiloxane.

[0070] The above thermosetting composition was stirred at room temperature of 25 °C until transparent and uniform, and then coated on a tinplate with a 20 μm wire bar to form a coating film with a thickness of 20 μm. The coated tinplate was placed in an oven at 100 °C for heating to obtain a cured film. The oven was an electrothermal constant temperature forced air drying oven.

[0071] The following several performance evaluations were carried out on the above thermosetting composition and its cured film.

[0072] (1) Curing speed

[0073] The shortest heating time required to cure the film in an oven at 100 °C was taken as the curing time. The shorter the curing time, the better the surface initiation performance. The curing degree of the cured film was evaluated according to the following criteria by the finger touch method.

[0074] Evaluation criteria:

[0075] 1 - Oily, not cured;

[0076] 2 - Oily on the surface, cured at the bottom layer;

[0077] 3 - Sticky on the surface, with heavy fingerprints after touching by hand;

[0078] 4 - Basically surface dry, slightly astringent after touching by hand, with faint fingerprints;

[0079] 5 - Completely cured, smooth surface, no fingerprints after touching by hand.

[0080] The test results of the curing degree are shown in Table 2.

[0081] Table 2

[0082]

[0083]

[0084] Among them, Comparative Compound 1: (All are hydrogen substitutions)

[0085] Comparative Compound 2: (All are hydrogen substitutions)

[0086] (2) Stability

[0087] The thermosetting composition is stored in an environment at 25°C, and its viscosity is tested every 24 hours. A rotary viscometer is used for the viscosity test. An 18# rotor is used, the temperature is maintained at 25°C, the rotation speed is set at 5 r / min, and the rotation time is 10 min. The smaller the viscosity increase, the better the stability of the thermal acid generator.

[0088] The test results of the viscosity (cps) are shown in Table 3 below.

[0089] Table 3

[0090]

[0091] As can be seen from the above two tables, for the deuterated N-(4-alkylbenzyl)-N,N-dialkylbenzenonium salt thermal acid generator of the present invention, after the same type of thermal initiator is applied to the thermosetting system under the same conditions, the thermosetting efficiency remains basically unchanged, but the stability is better than that of the non-deuterated N-(4-methoxybenzyl)-N,N-dimethylbenzenonium salt initiator of the same type, and it has broad application prospects.

[0092] The applicant declares that the present invention uses the above embodiments to illustrate the thermal acid generator of the present invention, its preparation method and application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A heat-producing acid agent, characterized in that, The thermal acid generator has the structure shown in formula (I): Among them, R1 represents deuterium or a straight-chain or branched-chain alkyl group having C1-C 10 and R2 and R3 independently represent hydrogen, deuterium, a linear or branched C1-C 10 linear or branched alkyl group or a deuterium-substituted C1-C 10 linear or branched alkyl group, and at least one of R2 and R3 is deuterium or a deuterium-substituted C1-C 10 linear or branched alkyl group; B represents a non-nucleophilic anion.

2. The heat-producing acidogen according to claim 1, wherein R1 represents hydrogen, methyl or ethyl; Preferably, R2 and R3 are independently selected from hydrogen, deuterium, methyl, deuterated methyl, ethyl or deuterated ethyl, and at least one of R2 and R3 is deuterium, deuterated methyl or deuterated ethyl; Preferably, B - preferably C n Q 2n+1 SO3 - , BQ4 - , SbQ6 - , AsQ6 - , PQ6 - or [B(C6Q5)4] - , wherein Q represents hydrogen or halogen, and n is an integer from 1 to 8; Preferably, the halogen is F, Cl, Br or I, preferably F.

3. The thermoacidogen according to claim 1 or 2, characterized in that, The thermal acid generator is selected from any one of the following compounds:

4. The preparation method of the thermoacidogen according to any one of claims 1-3, characterized in that, The preparation method includes the following steps: (1) The compound of formula II reacts with the compound of formula III to obtain the compound of formula IV, and the reaction formula is as follows: (2) The compound of formula IV reacts with an acid to obtain the thermal acid generator shown in formula (I), and the reaction formula is as follows: Wherein X represents a halogen.

5. The preparation method according to claim 4, characterized in that, The molar ratio of the compound of formula II to the compound of formula III in step (1) is 0.8 - 2:2 - 0.8; Preferably, the reaction in step (1) is carried out in a solvent, and the solvent is selected from any one or a combination of at least two of acetonitrile, dichloromethane, dichloroethane, benzene or toluene; Preferably, the temperature of the reaction in step (1) is 20 - 60 °C, and the reaction time is 3 - 8 h.

6. The preparation method according to claim 4 or 5, characterized in that, The molar ratio of the compound of formula IV to the acid in step (2) is 0.8 - 2:2:0.8; Preferably, the acid in step (2) is selected from hexafluorophosphoric acid, hexafluoroantimonic acid, hexafluoroarsenic acid, tetraphenylboric acid, tetrakis(pentafluorophenyl)boric acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, hexafluoroethanesulfonic acid, hexafluorobutanesulfonic acid, nonafluorobutanesulfonic acid or nonafluoropentanesulfonic acid; Preferably, the reaction in step (2) is carried out in a solvent, and the solvent is any one or a combination of at least two of acetone, cyclohexanone or butanone. Preferably, the reaction in step (2) is carried out at room temperature, and the reaction time is 0.5 - 2 h.

7. A thermosetting composition, characterized in that, The thermosetting composition includes the thermal acid generator according to any one of claims 1 - 3.

8. The thermosetting composition according to claim 7, characterized in that, The thermosetting composition, by mass, includes the following components:

9. The thermosetting composition according to claim 7, characterized in that, The epoxy resin is selected from bisphenol A, bisphenol F, phenolic epoxy resin, non-aromatic epoxy resin, alicyclic epoxy resin, epoxidized polysulfide and epoxy-functional acrylic resin or any combination thereof. Preferably, the leveling agent is selected from polyether-modified polydimethylsiloxane, poly(methyl)acrylate lauryl ester, poly(butyl)(methyl)acrylate, poly(2-ethylhexyl)(methyl)acrylate, or fluorinated polymers or polysiloxanes.

10. A cured film, characterized in that, The cured film is obtained by curing the thermosetting composition according to any one of claims 7 - 9.

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