CN115576171A - Negative photosensitive resin composition and method for preparing cured pattern - Google Patents

Abstract

The invention belongs to the technical field of photocuring, and particularly discloses a negative photosensitive resin composition and a cured film, wherein the negative photosensitive resin composition comprises the following components in parts by mass: the crosslinking agent comprises a first crosslinking agent and a second crosslinking agent, wherein the first crosslinking agent is an alkyloxy-containing compound, and the second crosslinking agent is an epoxy-containing compound; the reactive diluent comprises a first reactive diluent and a second reactive diluent, wherein the first reactive diluent is a monofunctional tertiary amine compound containing acrylic acid functional groups, and the second reactive diluent is a multifunctional compound containing more than two unsaturated double bonds; the preparation method of the cured pattern is that the negative photosensitive resin composition is formed by baking, exposing, developing and curing. The cured pattern formed by the invention has good adhesion and tensile properties.

Description

Negative photosensitive resin composition and method for preparing cured pattern

technical field

The invention relates to the field of photocuring technology, in particular to a negative photosensitive resin composition and a method for preparing a cured pattern.

Background technique

In electronic components such as integrated circuit components, organic EL components, and printed circuit boards, various resin films are required according to different requirements of electronic components, such as protective films used to prevent deterioration and damage of the components themselves; used to make the surface of components , A planarizing film for flattening wiring; an electrical insulating film for maintaining electrical insulation; an image separation film for separating the light emitting part; an optical film for light collection and diffusion, etc.

As a photosensitive resin composition capable of forming a resin film that can be used in various applications as described above, it can be divided into a positive photosensitive resin composition and a negative photosensitive resin composition according to the solubility of the photosensitive part in the photosensitive resin composition in a developer. combination. For the positive type, the exposed part dissolves in the developer; for the negative type, the exposed part does not dissolve in the developer, and the other part that is not exposed dissolves in the developer. The difference in the properties of the positive photosensitive resin composition and the negative photosensitive resin composition is mainly due to the difference in components such as resin polymers and crosslinking agents used in the process.

The existing synthesis and improvement of thermosetting resin polymers and the treatment of functional patterns mainly rely on photosensitizers to form positive resin compositions. Due to low sensitivity, thick films cannot be formed; resin polymers lose their alkali-soluble properties, Development in organic solvents presents an environmental hazard.

Contents of the invention

The object of the present invention is to provide a negative-type photosensitive resin composition and a method for preparing a cured pattern with high film retention rate, good adhesion and tensile properties in order to overcome the above-mentioned defects in the prior art.

In order to achieve the above purpose and other related purposes, the present invention provides the following technical solutions.

In the first aspect, the present invention provides a negative photosensitive resin composition, comprising the following components in parts by mass:

The crosslinking agent includes a first crosslinking agent and a second crosslinking agent, the first crosslinking agent is a compound containing an alkyloxy group, and the second crosslinking agent is a compound containing an epoxy group. In the present invention, the cross-linking agents are small molecular thermal cross-linking agents, which can reduce the thermal stress between the resins when the temperature rises and cure, thereby improving the overall substrate adhesion after curing. The first crosslinking agent will promote the alkali dissolution rate of the resin, and the second crosslinking agent will inhibit the alkali dissolution rate of the resin, and the simultaneous use of the two can balance the overall alkali dissolution rate of the composition.

The reactive diluent includes a first reactive diluent and a second reactive diluent, the first reactive diluent is a monofunctional tertiary amine compound containing acrylic acid functional groups, and the second reactive diluent is a compound containing two or more Polyfunctional compounds with saturated double bonds. The reactive diluents in the present invention are all small molecular reactive diluents, which can increase the flexibility of the entire cross-linked network during the photo-induced cross-linking reaction, and at the same time fill the gaps between the resins to increase the cross-linking density. The first type of reactive diluent can increase the binding degree of the resin and the photo-crosslinked network, thereby reducing the amount of total reactive diluent used, and the second type of reactive diluent mainly provides the properties of the photo-induced cross-linked network.

Further, the crosslinking agent is selected from at least one of the following technical features:

a1) The first crosslinking agent is selected from the following general structural formulas:

Among them, in formula B-1, R _b1 , R _b2 , R _b3 and R _b4 are each independently selected from C ₁ to C ₆ alkyl groups; in formula B-2, R _b5 , R _b6 , R _b7 , R _b8 , R _b9 and R _b10 are each independently selected from C ₁ to C ₆ alkyl groups;

a2) The second crosslinking agent is selected from at least one of the following general structural formulas,

Among them, in formula B-3, R _b11 and R _b12 are each independently selected from a hydrogen atom or a C ₁ -C ₆ alkyl group; in formula B-4, M _b is a C ₅ -C ₇ cyclohydrocarbyl group; formula B In -5, R _b13 , R _b14 and R _b15 are each independently selected from an epoxy group structure or a C ₁ -C ₆ alkyl group, and at least one of R _b13 , R _b14 and R _b15 is an epoxy group structure. .

Further, the crosslinking agent is selected from at least one of the following technical features:

a11) The first crosslinking agent is specifically selected from at least one of the following structures:

a21) The second crosslinking agent is specifically selected from at least one of the following structures:

Further, the reactive diluent is selected from at least one of the following technical features

b1) The first reactive diluent is selected from the following structural formulas:

其中，R_c1选自氢原子或C₁～C₆的烷基，R_c2和R_c3各自独立的选自C₁～C₆的烷基，X为氧原子或亚氨基，1≦q≦6；

Wherein, R _c1 is selected from a hydrogen atom or an alkyl group of C ₁ to C ₆ , R _c2 and R _c3 are each independently selected from an alkyl group of C ₁ to C ₆ , X is an oxygen atom or an imino group, and 1≦q≦6 ;

b2b2) The second reactive diluent is selected from at least one of the following general structural formulas:

Among them, in formula C-2, R _c4 is selected from a hydrogen atom or a C ₁ to C ₆ alkyl group, and X _c is selected from the following structures

Rc5选自氢原子或羟基，2≦m≦4，虚线为结合键；

Rc5 is selected from a hydrogen atom or a hydroxyl group, 2≦m≦4, and the dotted line is a bonding bond;

In formula C-3, R _c6 and R _c7 are each independently selected from a hydrogen atom or a C ₁ -C ₆ alkyl group, and M _c is a C ₅ -C ₁₀ cyclic hydrocarbon group;

虚线为连接键虚线为结合键。In formula C-4, R _c8 , R _c9 and R _c10 are each independently selected from a hydrogen atom or a C ₁ -C ₆ alkyl group, and Y _c is selected from the following structures

The dotted line is the connecting bond The dotted line is the bonding bond.

Further, the reactive diluent is selected from at least one of the following technical features:

b11) The first reactive diluent is selected from at least one of the following structures:

b21) The second reactive diluent is selected from at least one of the following structures:

Further, the photoinitiator includes a free radical photoinitiator and a co-initiator;

The free radical photoinitiator is selected from photoinitiator 819, photoinitiator TPO, photoinitiator TPO-L, photoinitiator OXE-01, photoinitiator OXE-02, photoinitiator OXE-03, photoinitiator OXE-04, Photoinitiator BP, Photoinitiator MBP, Photoinitiator MK, Photoinitiator EMK, Photoinitiator ITX, Photoinitiator DETX, Photoinitiator CTX, Photoinitiator CPTX, Photoinitiator BCIM at least one;

The co-initiator is selected from triethanolamine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dihydroxyethylaniline, N,N-dihydroxyethyl-p-toluidine Aniline, hydrogen donor NPG, (2-dimethylamino)ethyl benzoate, 4-dimethylaminobenzoic acid ethyl ester, 4,4',4"-tris(dimethylamino)triphenylmethane and other hydrogen donors at least one of

Further, the alkali-soluble resin polymer includes at least one of the following technical features:

c1) The weight average molecular weight of the alkali-soluble resin polymer is 3000-50000;

Preferred weight average molecular weight is 5000-30000,

Further preferred weight average molecular weight is 19000-24000

c2) the dissolution rate of the alkali-soluble resin polymer is

preferably for

Further preferred is

c3) the alkali-soluble resin polymer is selected from the following general structural formulas,

Wherein, the X1 is selected from at least _one of a benzene ring-containing structure and a siloxane-containing structure, and _Y1 is selected from at least one of a benzene ring-containing structure and a polyether-containing structure; the _R7 is a hydrogen atom or Acylation structure; said 0≦p≦2.

The alkali-soluble resin polymer also includes at least one of the following technical features:

d1) said X is selected from at least _one of the following structures

Wherein, the dotted line represents the binding bond;

d2) said Y is selected from at least _one of the following structures,

Wherein, the dotted line represents the binding bond;

d3) The acylation structure is prepared by an acylating agent and a hydroxyl group, and the acylating agent is selected from norbornene anhydride, maleic anhydride, methacrylic anhydride, allyl succinic anhydride, itaconic anhydride, tetrahydrophthalic anhydride At least one of diformic anhydride

Preferably, the acylating agent is selected from at least one of norbornene anhydride, maleic anhydride, and methacrylic anhydride.

Further, organic solvents are also included,

Preferably, the organic solvent is selected from anisole, toluene, xylene, trimethylbenzene, chlorinated benzene, dichlorobenzene, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl At least one of ketone, cyclopentanone, cyclohexanone, diacetone alcohol, γ-butyrolactone, N-methylpyrrolidone and ethyl lactate.

The second aspect of the present invention provides a method for preparing a cured pattern. The negative photosensitive resin composition described in any one of claims 1-9 is coated on a substrate, and after baking, exposure, development, and curing, the obtained Solidify the pattern.

Further, at least one of the following technical features is also included:

e1) The baking temperature is 80-120°C;

e2) The baking time is 1 to 10 minutes; such as 3 minutes

e3) the exposure uses a 200W ultraviolet mercury lamp exposure machine;

e4) The developing solution adopts 2.38% tetramethylammonium hydroxide aqueous solution;

e5) the curing temperature is 160-400°C;

e6) The curing time is 1 to 3 hours, such as 1.5 hours.

e7) The thickness of the cured film is 5-20um. Such as 7um.

Compared with prior art, the beneficial effect of the present invention is:

The present invention can provide a low-temperature-curable negative photosensitive resin composition that can be developed using alkali after exposure. When the negative-type photosensitive resin composition is used in combination with a crosslinking agent and a reactive diluent, it can obtain a higher developing film retention rate under low energy during exposure, and the cured film has good adhesion and tensile properties.

detailed description

Unless otherwise stated, implied from the context, or customary in the art, all parts and percentages in this application are by weight and the testing and characterization methods used are current as of the filing date of this application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are hereby incorporated by reference in their entirety, and equivalent patent families are also incorporated by reference, especially those disclosed by these documents with respect to the state of the art. Synthetic techniques, product and process design, definitions of polymers, comonomers, initiators or catalysts, etc. If the definition of a specific term disclosed in the prior art is inconsistent with any definition provided in the present application, the definition of the term provided in the present application shall prevail.

Numerical ranges in this application are approximations and therefore may include values outside the range unless otherwise indicated. Numerical ranges include all values from the lower value to the upper value in increments of 1 unit provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a composition, physical or other property (such as molecular weight, melt index, etc.) is stated as 100 to 1000, it is meant to expressly recite all individual values, such as 100, 101, 102, etc., and all subranges, such as 100 to 166, 155 to 170, 198 to 200, etc. For ranges containing numerical values less than one or containing fractional numbers greater than one (eg, 1.1, 1.5 etc.), one unit is considered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is generally considered to be 0.1. These are only specific examples of what is intended to be expressed, and the range between the lowest and highest values enumerated All possible combinations of values are considered to be expressly stated in this application. The numerical ranges within this application provide, inter alia, calcium-containing filler content, agitation temperature, and various characteristics and properties of these components.

When used with reference to a chemical compound, unless expressly stated otherwise, the singular includes all isomeric forms and vice versa (eg, "hexane" includes all isomers of hexane, individually or collectively). In addition, references to "a", "an" or "the" include plural forms unless expressly stated otherwise.

The terms "comprising", "comprising", "having" and their derivatives do not exclude the existence of any other components, steps or processes, and have nothing to do with whether these other components, steps or processes are disclosed in the present application. To remove any doubt, all compositions in this application using the terms "comprising", "comprising", or "having" may contain any additional additives, excipients or compounds, unless expressly stated otherwise. Conversely, the term "consisting essentially of" excludes from the scope of any hereinafter recitation of that term, other than those necessary for operational performance. The term "consisting of" does not include any component, step or process not specifically described or listed. Unless expressly stated otherwise, the term "or" refers to the listed members individually or to any combination thereof.

Example

The embodiments of the present invention will be described in detail below. This embodiment is implemented under the premise of the technical solution of the present invention, and detailed implementation methods and specific operating procedures are provided, but the protection scope of the present invention is not limited to the following Example.

The following are the various components used in the examples and comparative examples

1. Alkali-soluble resin polymer A

Synthesis of Alkali-Soluble Resin Polymer A1

2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.025mol), 4,4'-diaminodiphenyl ether (0.020mol), 1,3-bis(3-aminopropyl ) Tetramethyldisiloxane (0.005mol), 4,4'-diphenyl ether dianhydride (0.49mol), dissolved in N,N-dimethylformamide 190g, stirred at room temperature for 12 hours, after 85 After heating at reflux for 4 hours at ℃, cool to room temperature, add norbornene anhydride (0.04mol) and methacrylic anhydride (0.01mol), stir and react at -20～0℃ for 24 hours, filter, precipitate and dry to obtain resin polymer Material A1, molecular weight 24000.

Resin polymer A1 dissolution rate (ADR) measurement: resin polymer A1 is immersed in the aqueous solution of 2.38% tetramethylammonium hydroxide (TMAH), records ADR as

Synthesis of Alkali-Soluble Resin Polymer A2

2,2-bis(4-hydroxy-3-aminophenyl)propane (0.015mol), 4,4'-diaminodiphenyl ether (0.035mol), 4,4'-biphenyl ether dianhydride (0.34mol ), 3,3',4,4'-benzophenonetetraacid dianhydride (0.14mol), dissolved in 220g of N,N-dimethylformamide, stirred at room temperature for 12 hours, and heated under reflux at 70°C for 6 Cool to room temperature after 1 hour, add maleic anhydride (0.025mol), stir and react at 80-100°C for 6 hours, filter, precipitate and dry to obtain resin polymer A2 with a molecular weight of 19,000.

Resin polymer A2 dissolution rate (ADR) measurement: resin polymer A2 is immersed in the TMAH aqueous solution of 2.38%, records ADR as

Synthesis of Alkali-Soluble Resin Polymer A3

2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.02mol), 4,4'-diaminodiphenyl ether (0.03mol), 3,3',4,4'-di Phenylsulfone tetracarboxylic dianhydride (0.024mol), 3,3',4,4'-biphenyltetracarboxylic dianhydride (0.025mol), N,N-dimethylformamide diethyl acetal ( 0.2mol), dissolved in 230g of N-methylpyrrolidone, stirred at room temperature for 12 hours, heated at reflux at 80°C for 5 hours, cooled to room temperature, added maleic anhydride (0.025mol) and methacrylic anhydride (0.015mol) and stirred , reacted at 30-50°C for 12 hours, filtered, precipitated, and dried to obtain resin polymer A3 with a molecular weight of 21,000.

Resin polymer A3 dissolution rate (ADR) measurement: resin polymer A3 is immersed in the aqueous solution of 2.38%TMAH, records ADR as

2. Cross-linking agent B

B1: Tetramethoxymethyl glycoluril

B2: Bisphenol A diglycidyl ether

3. Active diluent C

C1; dimethylaminoethyl methacrylate

C2: Triethylene glycol dimethacrylate

C3: Trimethallyl isocyanate

4. Photoinitiator combination D

D1, Photoinitiator: OXE-01, OXE-02, 819, EMK

Among them, the mass ratio of OXE-01, OXE-02, 819 and EMK is 2:1:5:1;

D2, photoinitiator: BP, ITX, EMK, hydrogen donor NPG,

Among them, the mass ratio of BP, ITX, EMK and NPG is 5:2:1:3;

D3, photoinitiator: 819, BP, ITX, hydrogen donor NPG

Among them, the mass ratio of 819, BP, ITX and NPG is 5:3:2:3;

5. Organic solvents

γ-butyrolactone 230 parts.

Example 1

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, then use the spin coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness. The power used is 200W UV mercury lamp exposure machine for pattern exposure, develop in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute from room temperature after curing at 180°C for 0.5 hours and 250°C for 2 hours, then at 2°C per minute Cool down to 150°C at a rate, and then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 190mJ, a developing film retention rate of 94%, an adhesion of 100/100, and a tensile strength of >120MPa. Elongation at break>10%, see Table 1 and Table 2 for specific results.

Example 2

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, and then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 195mJ, a developing film retention rate of 85%, an adhesion of 100/100, and a tensile strength of >120MPa. Elongation>10%, the specific results are shown in Table 1 and Table 2.

Example 3

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 210mJ, a developing film retention rate of 87%, an adhesion of 100/100, and a tensile strength of >120MPa. Elongation>10%, the specific results are shown in Table 1 and Table 2.

Example 4

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, and then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 205mJ, a developing film retention rate of 91%, an adhesion of 100/100, and a tensile strength of >120MPa. Elongation>10%, the specific results are shown in Table 1 and Table 2.

Example 5

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, and then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 235mJ, a developing film retention rate of 86%, an adhesion of 100/100, and a tensile strength of >120MPa. Elongation>10%, the specific results are shown in Table 1 and Table 2.

Example 6

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 195mJ, a developing film retention rate of 89%, an adhesion of 100/100, and a tensile strength of >120MPa. Elongation>10%, the specific results are shown in Table 1 and Table 2.

Example 7

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, and then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 220mJ, a developing film retention rate of 92%, an adhesion of 100/100, and a tensile strength of >120MPa. Elongation>10%, the specific results are shown in Table 1 and Table 2.

Example 8

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 290mJ, a developing film retention rate of 89%, an adhesion of 100/100, and a tensile strength of >120MPa. Elongation>10%, the specific results are shown in Table 1 and Table 2.

Example 9

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 245mJ, a developing film retention rate of 88%, an adhesion of 100/100, and a tensile strength of >120MPa. Elongation>10%, the specific results are shown in Table 1 and Table 2.

Comparative example 1

A negative photosensitive resin composition:

Alkali-soluble resin polymer A1 100 parts

Photoinitiator combination D1 12 parts

γ-butyrolactone 230 parts

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 380mJ, a developing film retention rate of 79%, an adhesion of 95/100, a tensile strength of 98MPa, and a breaking elongation The growth rate was 7.1%, and the specific results are shown in Table 1 and Table 2.

Comparative example 2

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, and then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 415mJ, a developing film retention rate of 80%, an adhesion of 88/100, a tensile strength of 102MPa, and an elongation at break. The growth rate is 4.4%. The specific results are shown in Table 1 and Table 2.

Comparative example 3

A negative photosensitive resin composition:

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute, after curing from room temperature for 0.5 hours at 180°C and 2 hours at 250°C, then at a rate of 2°C per minute Cool down to 150°C, and then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 395mJ, a developing film retention rate of 68%, an adhesion of 93/100, a tensile strength of 87MPa, and a breaking elongation The growth rate is 5.3%. The specific results are shown in Table 1 and Table 2.

Comparative example 4

A negative photosensitive resin composition:

Alkali-soluble resin polymer A3 100 parts

Photoinitiator combination D3 13 parts

γ-butyrolactone 230 parts

Preparation method of cured pattern

Fully dissolve the above-mentioned components, use the spin-coating method on a 4-inch silicon wafer, adjust the rotation speed, and bake on a contact hot plate at 100°C for 4 minutes to form a photosensitive film with a specific film thickness, using a power of 200W The UV mercury lamp exposure machine is used for pattern exposure, developed in TMAH 2.38% solution, at a heating rate of 5 degrees Celsius per minute from room temperature after 0.5 hours at 180 degrees Celsius and 2 hours at 250 degrees Celsius for 2 hours, and at a rate of 2 degrees Celsius per minute Cool down to 150°C, and then cool down to room temperature at 5°C per minute to obtain a 7um cured film with a photosensitivity of 340mJ, a developing film retention rate of 73%, an adhesion of 95/100, a tensile strength of 99MPa, and a breaking elongation The growth rate is 6.5%. The specific results are shown in Table 1 and Table 2.

The specific compositions and related properties of the above-mentioned Examples 1-9 and Comparative Examples 1-4 are shown in Table 1 below.

Photosensitivity: After the substrate is exposed during development, the minimum exposure energy that maintains the film thickness change less than 1% within 10s.

Film retention rate: Based on the exposed area just exposed after development, and the remaining film thickness T1 after development at the unexposed area, the development film retention rate is T1/original film thickness T.

Adhesion: the adhesion substrate is copper, with reference to the standard ASTM D3359, and the test is carried out with a cross-cutting knife

Tensile strength and elongation at break: refer to the standard ASTM D882, and use a general tensile testing machine for testing

Table 1 embodiment and comparative ratio proportioning

Table 2 embodiment and comparative example performance

Compared with Comparative Examples 1-3, the difference between Examples 1-9 and Comparative Examples 1-3 is that two different crosslinking agents and three different reactive diluents are used in the resin composition of Examples 1-9. Comparative Example 1 In -3, the cross-linking agent and reactive diluent are not used in combination at the same time. Compared with Comparative Example 4, the difference between Examples 1-9 and Comparative Example 4 is that two different crosslinking agents and three different reactive diluents are used in the resin composition of Examples 1-9, while Comparative Example 4 only uses Three different neutral active diluents.

And in embodiment 1-9, its photosensitivity is between 190-290mJ, and the maximum value is 290mJ, and the minimum value is 190mJ; 88%, its adhesion is 100/100, its tensile strength is greater than 120MPa, and its elongation at break is greater than 10%.

In comparative examples 1-4, its photosensitivity is between 340-410mJ, the maximum value is 410mJ, and the minimum value is 340mJ; its developing film retention rate is between 68-80%, the maximum value is 80%, and the minimum value is 68%, its adhesion is 88/100-95/100, its tensile strength is 87-102MPa, and its elongation at break is 4.4-7.1%.

Therefore, the negative photosensitive resin composition is used in combination with different crosslinking agents and different reactive diluents, which can obtain a high film retention rate of development under low energy during exposure, and the cured film has good adhesion. and tensile properties.

The above-mentioned cured film can be applied to industries such as semiconductors and electronic products, and specifically can be applied to semiconductor elements, packaging substrates, metal insulating layers, surface protection layers, stress buffer layers, and device support layers of printed circuit boards.

Claims (11)

1. a negative photosensitive resin composition, is characterized in that, comprises each component of following mass parts:

The crosslinking agent includes a first crosslinking agent and a second crosslinking agent, the first crosslinking agent is a compound containing an alkyloxy group, and the second crosslinking agent is a compound containing an epoxy group; The reactive diluent includes a first reactive diluent and a second reactive diluent, the first reactive diluent is a monofunctional tertiary amine compound containing acrylic acid functional groups, and the second reactive diluent is a compound containing two or more Polyfunctional compounds with saturated double bonds. 2. negative photosensitive resin composition according to claim 1, is characterized in that, described linking agent also comprises at least one in the following technical characteristics: a1) The first crosslinking agent is selected from at least one of the following general structural formulas,

Among them, in formula B-1, R _b1 , R _b2 , R _b3 and R _b4 are each independently selected from C ₁ to C ₆ alkyl groups; in formula B-2, R _b5 , R _b6 , R _b7 , R _b8 , R _b9 and R _b10 are each independently selected from C ₁ to C ₆ alkyl groups; a2) The second crosslinking agent is selected from at least one of the following general structural formulas,

Wherein, in formula B-3, R _b11 and R _b12 are each independently selected from a hydrogen atom or a C ₁ -C ₆ alkyl group; In formula B-4, M _b is a C ₅ -C ₇ cycloalkyl group; In formula B-5, R _b13 , R _b14 and R _b15 are each independently selected from an epoxy group structure or a C ₁ -C ₆ alkyl group, and at least one of R _b13 , R _b14 and R _b15 is an epoxy group structure . 3. The negative-type photosensitive resin composition according to claim 2, wherein the crosslinking agent is selected from at least one of the following technical characteristics: a11) The first crosslinking agent is specifically selected from at least one of the following structures:

a21) The second crosslinking agent is specifically selected from at least one of the following structures:

4. The negative photosensitive resin composition according to claim 1, wherein the reactive diluent is selected from at least one of the following technical characteristics: b1) The first reactive diluent is selected from the following structural formulas:

Wherein, R _c1 is selected from a hydrogen atom or an alkyl group of C ₁ to C ₆ , R _c2 and R _c3 are each independently selected from an alkyl group of C ₁ to C ₆ , X is an oxygen atom or an imino group, and 1≦q≦6 ; b2) The second reactive diluent is selected from at least one of the following general structural formulas:

Among them, in formula C-2, R _c4 is selected from a hydrogen atom or a C ₁ to C ₆ alkyl group, and X _c is selected from the following structures

Rc5 is selected from a hydrogen atom or a hydroxyl group, 2≦m≦4, and the dotted line is a bonding bond; In formula C-3, R _c6 and R _c7 are each independently selected from a hydrogen atom or a C ₁ -C ₆ alkyl group, and M _c is a C ₅ -C ₁₀ cyclic hydrocarbon group; In formula C-4, R _c8 , R _c9 and R _c10 are each independently selected from a hydrogen atom or a C ₁ -C ₆ alkyl group, and Y _c is selected from the following structures

The dotted line is the connecting bond The dotted line is the bonding bond. 5. negative photosensitive resin composition according to claim 4, is characterized in that, described reactive diluent is selected from at least one in the following technical characteristics: b11) The first reactive diluent is selected from at least one of the following structures:

b21) The second reactive diluent is selected from at least one of the following structures:

6. according to the described negative photosensitive resin composition of claim 1, it is characterized in that, described photoinitiator comprises free radical photoinitiator and co-initiator; The free radical photoinitiator is selected from photoinitiator 819, photoinitiator TPO, photoinitiator TPO-L, photoinitiator OXE-01, photoinitiator OXE-02, photoinitiator OXE-03, photoinitiator OXE-04, Photoinitiator BP, Photoinitiator MBP, Photoinitiator MK, Photoinitiator EMK, Photoinitiator ITX, Photoinitiator DETX, Photoinitiator CTX, Photoinitiator CPTX, Photoinitiator BCIM at least one; The co-initiator is selected from triethanolamine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dihydroxyethylaniline, N,N-dihydroxyethyl-p-toluidine Aniline, NPG, (2-dimethylamino)ethyl benzoate, 4-dimethylaminobenzoic acid ethyl ester, 4,4',4"-tris(dimethylamino)triphenylmethane and other hydrogen donors at least one. 7. negative photosensitive resin composition according to claim 1, is characterized in that, described alkali-soluble resin polymer comprises at least one in the following technical feature: c1) The weight average molecular weight of the alkali-soluble resin polymer is 3000-50000; c2) the dissolution rate of the alkali-soluble resin polymer is

c3) the alkali-soluble resin polymer is selected from the following general structural formulas,

Wherein, the X1 is selected from at least _one of a benzene ring-containing structure and a siloxane-containing structure, and _Y1 is selected from at least one of a benzene ring-containing structure and a polyether-containing structure; the _R7 is a hydrogen atom or Acylation structure; said 0≦p≦2. 8. The negative-type photosensitive resin composition according to claim 7, characterized in that, the alkali-soluble resin polymer also includes at least one of the following technical characteristics: d1) said X is selected from at least _one of the following structures:

Wherein, the dotted line represents the binding bond; d2) said Y is selected from at least _one of the following structures,

Wherein, the dotted line represents the binding bond; d3) The acylation structure is prepared by reacting an acylating agent with a hydroxyl group, and the acylating agent is selected from norbornene anhydride, maleic anhydride, methacrylic anhydride, allyl succinic anhydride, itaconic anhydride, tetrahydro-ortho at least one of phthalic anhydride. 9. The negative photosensitive resin composition according to any one of claims 1-8, further comprising an organic solvent. 10. A method for preparing a cured pattern, characterized in that, the negative-type photosensitive resin composition according to any one of claims 1-9 is coated on a substrate, and the cured pattern is obtained through baking, exposure, development, and curing. . 11. The method for preparing a cured pattern according to claim 10, further comprising at least one of the following technical features: e1) The baking temperature is 80-120°C; e2) The baking time is 1 to 10 minutes; e3) the exposure uses a 200W ultraviolet mercury lamp exposure machine; e4) The developing solution adopts 2.38% tetramethylammonium hydroxide aqueous solution; e5) The curing temperature is 160-400°C.