A photosensitive resin composition and its application

Abstract

The present invention discloses a photosensitive resin composition and its application, the photosensitive resin composition comprises 15-30 parts of an alkali-soluble photosensitive epoxy resin with an acid value of 60-200KOH / g; 0-15 parts of a second epoxy resin; 0-5 parts of an alkali-soluble phosphorus-containing polyurethane acrylic resin; 0-25 parts of a toughening agent; 0-2 parts of a photoinitiator; 0-2 parts of a thermosetting agent; 10-70 parts of an inorganic filler; and 10-35 parts of a solvent. The photosensitive resin composition provided by the present invention introduces an alkali-soluble phosphorus-containing polyurethane acrylic resin, and assists with a toughening agent to improve film-forming properties and flexibility as well as elongation at break after film formation, so that the photosensitive resin composition can meet more stringent performance requirements of printed circuit boards and meet the application of more scenarios.

Description

Technical Field

[0001] The invention relates to the technical field of photoresists, and in particular to a photosensitive resin composition and application thereof. Background Art

[0002] Photoresist is a type of resin composition with photosensitive chemical action (or sensitive to electron energy). It is a medium for transferring ultraviolet exposure or electron beam exposure patterns. Its English name is resist, which can also be translated as anti-corrosion agent, etc. It is widely used in integrated circuits (IC), packaging, micro-electromechanical systems (MEMS)\optoelectronic devices / photonics, flat panel displays (LED / LCD / OLED), solar photovoltaic (SolarPV) and other fields. In electronic packaging, permanent masking resist is applied to the printed wiring board to prevent corrosion of the conductor layer or maintain electrical insulation between conductor layers. With the miniaturization and high density of electronic equipment, the permanent masking resist used in printed circuit boards also has a higher demand for micro-processing. In addition, with the high multi-layering of substrates and the large-scale chips, it is necessary to have high hardness, high flexibility, and excellent flame retardant properties. In particular, during temperature cycle experiments, it is required to have better fracture resistance than before.

[0003] At present, traditional photosensitive resin compositions have problems such as high brittleness, low resolution, and relatively weak insulation resistance, which seriously limit their application. The performance of the photosensitive resin composition mainly depends on the structure and properties of the main resin. The photosensitive resin composition used as a photoresist mainly uses acrylic acid and anhydride-modified epoxy resin as the main resin. It has a high cross-linking density and the material is relatively brittle after curing. The obtained dry film often has low adhesion, high hardness, high brittleness, poor flexibility, and low elongation at break, which cannot meet the needs of practical applications. Therefore, it is urgent to develop a photosensitive resin composition with high adhesion to the substrate, high hardness, high flexibility, high fracture resistance, and excellent flame retardant properties, and a dry film using the same. At present, there are two main ways to solve the toughness of photosensitive dry films: physical modification and chemical modification. Physical modification is mainly achieved by adding some inorganic particles such as BaSO 4 、Gas-phase SiO 2 For example, in patent CN90105419.4, photosensitizer, thermal initiator and gas phase SiO 2 and styrene; or adding resins with good flexibility, such as the addition of carboxyl-containing polyurethane resin in patent CN200680007163.6. Chemical modification mainly introduces some flexible chains into the molecular chain of the main resin, such as patent CN201811494319.9, which obtains fatty acid-containing alkali-soluble light-curing epoxy resin by introducing fatty acid-modified epoxy resin, thereby improving flexibility.

[0004] Although the above methods can effectively improve the flexibility of the system, there are still some problems. For example, physical modification may cause uneven dispersion of the system during use, difficulty in long-term storage, phase separation, and difficulty in uniform film formation during coating. Chemical modification methods may design multiple side reactions during the synthesis process, reducing the purity of the product. Summary of the invention

[0005] In view of the above technical problems, the present invention provides a photosensitive resin composition and application thereof.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] In one aspect, the present invention provides a photosensitive resin composition, comprising:

[0008] (A) component: 15 to 30 parts of an alkali-soluble photosensitive epoxy resin having an acid value of 60 to 200 KOH / g;

[0009] (B) component: 0 to 15 parts of a second epoxy resin;

[0010] (C) component: 0-5 parts of alkali-soluble phosphorus-containing polyurethane acrylic resin;

[0011] (D) component: 0 to 25 parts of toughening agent;

[0012] (E) component: 0-2 parts of photoinitiator;

[0013] (F) Component: 0-2 parts of thermal curing agent;

[0014] (G) component: 10 to 70 parts of inorganic filler;

[0015] (H) Component: 10 to 35 parts of solvent.

[0016] As a preferred embodiment, the photosensitive resin composition comprises:

[0017] (A) component: 20 to 30 parts of an alkali-soluble photosensitive epoxy resin having an acid value of 60 to 200 KOH / g;

[0018] (C) component: 3 to 5 parts of alkali-soluble phosphorus-containing polyurethane acrylic resin;

[0019] (F) Component: 0-2 parts of thermal curing agent;

[0020] (G) component: 35-70 parts of inorganic filler;

[0021] (H) component: 25-35 parts of solvent;

[0022] Preferably, the mass ratio of the component (A) to the component (C) is 1:0.1-10.

[0023] As a preferred embodiment, the photosensitive resin composition comprises:

[0024] (A) component: 20 to 30 parts of an alkali-soluble photosensitive epoxy resin having an acid value of 60 to 200 KOH / g;

[0025] (B) component: 5 to 15 parts of the second epoxy resin;

[0026] (D) component: 10 to 25 parts of toughening agent;

[0027] (E) component: 0-2 parts of photoinitiator;

[0028] (F) Component: 0-2 parts of thermal curing agent;

[0029] (G) component: 35-70 parts of inorganic filler;

[0030] (H) Component: 25 to 35 parts of solvent.

[0031] As a preferred embodiment, the alkali-soluble photosensitive epoxy resin is an epoxy resin containing a photosensitive group and an alkali-soluble group on the molecular chain; the photosensitive group is selected from at least one of a carbonyl group, a carboxyl group, a peroxide group and a carbon-carbon double bond; the alkali-soluble group is selected from at least one of a carboxyl group, an acid anhydride group and an ester group;

[0032] Preferably, the alkali-soluble photosensitive epoxy resin is a phenolic epoxy resin modified by an organic acid containing a carbon-carbon double bond or an acid anhydride containing a carbon-carbon double bond;

[0033] Specifically, the alkali-soluble photosensitive epoxy resin is selected from at least one of alkali-soluble photosensitive o-cresol epoxy resin, alkali-soluble photosensitive phenol novolac epoxy resin, alkali-soluble photosensitive bisphenol A novolac epoxy resin, alkali-soluble photosensitive BPA novolac epoxy resin, alkali-soluble photosensitive dicyclopentadiene phenol type epoxy resin, alkali-soluble photosensitive phenol biphenyl type epoxy resin and alkali-soluble photosensitive XYLOK novolac epoxy resin;

[0034] Preferably, the alkali-soluble photosensitive o-cresol epoxy resin has a structure represented by the following formula (1):

[0035]

[0036] In formula (1), 100≤m≤400;

[0037] Preferably, the alkali-soluble photosensitive phenol novolac epoxy resin has a structure shown in the following formula (2):

[0038]

[0039] In formula (2), 50≤n≤200;

[0040] Preferably, the alkali-soluble photosensitive epoxy resin has a weight average molecular weight Mw of 5000 to 50000 g / mol.

[0041] In the technical solution of the present invention, the acid value represents the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of chemical substances.

[0042] In the technical solution of the present invention, the type of the second epoxy resin is not limited, as long as it is different from component (A), for example, a bisphenol F novolac type epoxy resin.

[0043] As a preferred embodiment, the preparation method of the alkali-soluble phosphorus-containing polyurethane acrylic resin comprises the following steps:

[0044] (1) reacting polyester polyol or polyether polyol, isocyanate polymer, alcohol monomer with unsaturated double bonds having free radical polymerizability, (meth) alkyl acrylate monomer, catalyst and inhibitor to obtain alkali-soluble polyurethane acrylate;

[0045] (2) reacting the obtained alkali-soluble polyurethane acrylate with a phosphoric acid compound (P(O)-OH) in a solvent to obtain the alkali-soluble phosphorus-containing polyurethane acrylate.

[0046] Preferably, in step (1), the reaction temperature is 70 to 120°C;

[0047] In some specific embodiments, the polyester polyols include Dynacoll 7110 and Dynacoll 7130 of Evonik Degussa, Priplast 3196, Priplast 1838, Priplast 3294 and Priplast 3238 of Croda Polyol, PCL220, PCL220N, PCL220L and PCL220CP of Daicel, etc.

[0048] In some specific embodiments, the polyether polyols include C2040 and C2140 of Wanhua Chemical, PTMG650, PTMG850 and PTMG1000 of Mitsubishi Chemical, etc.

[0049] In certain specific embodiments, in step (1), the mass ratio of the polyester polyol or polyether polyol, isocyanate polymer, alcohol monomer with unsaturated double bonds having free radical polymerizability, (meth) alkyl acrylate monomer, catalyst and inhibitor is 130-170: 130-170: 10-30: 170-200: 0.1-0.5: 0.1-0.5;

[0050] Preferably, in step (2), the reaction temperature is 70-100°C;

[0051] Preferably, in step (2), the reaction is carried out until the content of -NCO in the reaction system is ≤ 0.2%; in certain specific embodiments, the reaction time is 1 to 5 hours.

[0052] In certain specific embodiments, the isocyanate polymer is an isocyanate trimer or an isocyanate dimer, specifically selected from at least one of hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI) and isophorone diisocyanate (IPDI);

[0053] Preferably, the (meth)acrylic acid alkyl ester monomer is selected from at least one of lauryl methacrylate, lauryl acrylate and isobornyl methacrylate;

[0054] Preferably, the polymerization inhibitor is selected from at least one of p-hydroxyanisole and hydroquinone;

[0055] Preferably, the alcohol monomer having an unsaturated double bond that is free radical polymerizable is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate;

[0056] Preferably, the solvent is selected from at least one of anhydrous polypropylene glycol and N,N-dimethylformamide;

[0057] Preferably, the phosphoric acid compound (P(O)-OH) is selected from at least one of triethylene glycol phosphate, diphenyl phosphoric acid, bis(4-methylphenyl)phosphoric acid, bis(3-methylphenyl)phosphoric acid, bis(4-methoxyphenyl)phosphoric acid, bis(4-trifluoromethyl-phenyl)phosphoric acid, bis(1-methylnaphthyl)phosphoric acid and bis(2-methylnaphthyl)phosphoric acid.

[0058] As a preferred embodiment, the toughening agent is selected from at least one of carboxyl-terminated liquid nitrile rubber, flexible epoxy resin and hydroxyl-terminated polydimethylsiloxane, and more preferably at least two of carboxyl-terminated liquid nitrile rubber, flexible epoxy resin and hydroxyl-terminated polydimethylsiloxane;

[0059] Preferably, the flexible epoxy resin is an epoxy resin containing a flexible segment or group on the molecular chain; the flexible segment or group is selected from at least one of a sulfone group, a thioether bond, a methyl group, a carbonyl group and a trifluoromethyl group.

[0060] In the technical solution of the present invention, the photoinitiator is not particularly limited, and can be specifically selected from at least one of an aromatic ketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator, a titanocene-based photopolymerization initiator, and an oxime ester-based photopolymerization initiator;

[0061] Specifically, from the viewpoint of obtaining clarity and rectangular patterns, it is preferred to use an aromatic ketone-based photopolymerization initiator or a thioxanthone-based photopolymerization initiator; as the aromatic ketone-based photopolymerization initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1 is preferred; as the thioxanthone-based photopolymerization initiator, 2,4-diethylthioxanthone is preferred;

[0062] Specifically, in order to improve the sensitivity, it is preferred to use an oxime ester photopolymerization initiator; as the above-mentioned oxime ester photopolymerization initiator, 2-(acetoxyiminomethyl)thioxanthen-9-one, (1,2-octanedione, 1-[4-(phenylthio)phenyl, 2-(o-benzoyl oxime))], ethyl ketone, 1-(o-acetyl oxime), among which ethyl ketone, 1-(o-acetyl oxime) is most preferred;

[0063] In the technical solution of the present invention, the thermosetting agent is not particularly limited, and is preferably a thermosetting agent having a phenolic hydroxyl group or a thermosetting agent having a hydroxymethylamino group, and specific examples thereof include biphenol and its derivatives, melamine, poly(N-hydroxymethyl)melamine, poly(N-hydroxymethylglycoluril), poly(N-hydroxymethylbenzoguanamine), and the like.

[0064] As a preferred embodiment, the inorganic filler is selected from silicon dioxide (SiO2), aluminum oxide (Al2O3), titanium oxide (TiO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), silicon nitride (Si 3 N4), barium titanate (BaO·TiO 2 ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga 2 O3), spinel (MgO·Al2O3), mullite (3Al2O 3 ·2SiO 2 )、cordierite (2MgO·2Al 2 O 3 / 5SiO 2 )、Talc(3MgO·4SiO 2 ·H 2 O), aluminum titanate (TiO 2 ·Al2O3), yttria-containing zirconium oxide (Y2O3·ZrO2), barium silicate (BaO·8SiO 2), boron nitride (BN), calcium carbonate (CaCO3), barium sulfate (BaSO4), calcium sulfate (CaSO 4 ), at least one of hydrotalcite, mica, carbon (C), bentonite and montmorillonite;

[0065] Preferably, the particle size of the inorganic filler is 0.1 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.1 to 5 μm, and particularly preferably 0.1 to 1 μm;

[0066] Specifically, from the viewpoint of improving heat resistance, the inorganic filler is preferably silicon dioxide;

[0067] Specifically, from the viewpoint of improving solder heat resistance, crack resistance (thermal shock resistance), and adhesive strength, the inorganic filler is preferably barium sulfate fine particles.

[0068] Specifically, from the viewpoint of improving the anti-agglomeration property, the inorganic filler is surface-treated in advance with alumina and / or an organic silane coupling agent.

[0069] As a preferred embodiment, the solvent is selected from at least one of alcohols, glycol ethers and esters.

[0070] As a preferred embodiment, the invention further comprises (I) component: an auxiliary agent; the auxiliary agent comprises at least one of a pigment, a leveling agent and a defoaming agent;

[0071] Specifically, the pigment includes phthalocyanine blue, phthalocyanine green, iodine green, malachite green, crystal violet, carbon black and the like.

[0072] In another aspect, the present invention provides a photosensitive film prepared from the above-mentioned photosensitive resin composition; the photosensitive film is obtained by curing a solution including the above-mentioned photosensitive resin composition;

[0073] Preferably, the thickness of the photosensitive film is 5 to 200 μm, more preferably 15 to 60 μm, and most preferably 20 to 50 μm;

[0074] Preferably, the solvent in the solution comprising the above-mentioned photosensitive resin composition is selected from at least one of acetone and carbitol acetate;

[0075] Preferably, the curing is thermal curing; the thermal curing condition is 80-130° C. for 3-10 min.

[0076] In another aspect, the present invention provides a photosensitive resin laminate including a support and the photosensitive film disposed on the support.

[0077] Preferably, a protective film is provided on the photosensitive film.

[0078] In some specific embodiments, the support is prepared from a polymer film having heat resistance and solvent resistance such as polypropylene and polyethylene;

[0079] In some specific embodiments, the protective film is prepared from a heat-resistant and solvent-resistant polymer film such as polypropylene and polyethylene;

[0080] Preferably, the photosensitive resin laminate further includes an intermediate layer; the intermediate layer includes at least one of a buffer layer, an adhesive layer, a light absorbing layer and a gas barrier layer.

[0081] In another aspect, the present invention provides an application of the photosensitive resin composition in the field of electronic packaging, specifically, an application in the preparation of photoresist.

[0082] The above technical solution has the following advantages or beneficial effects:

[0083] The present invention further introduces alkali-soluble phosphorus-containing polyurethane acrylate into the traditional alkali-soluble modified epoxy resin, which can not only effectively improve the viscosity, insulation, flame retardancy and weather resistance of the photosensitive resin composition to meet the stringent requirements of printed circuit boards, but also improve the film-forming property and flexibility of the photosensitive resin composition and the elongation at break of the photosensitive dry film to meet the application of more scenarios.

[0084] The present invention introduces flexible epoxy resin and liquid nitrile rubber as composite toughening agents into the traditional alkali-soluble modified epoxy resin to improve the toughness of the photosensitive resin composition ink and its dry film. Among them, the liquid nitrile rubber can significantly improve the toughness of the resin system by using the flexible structure in the main chain, but when only the liquid nitrile rubber is used, it is easy to form a phase separation with the main resin alkali-soluble epoxy resin when its content reaches a certain limit, and the addition of the flexible epoxy resin can not only improve the toughness of the solder mask ink system, but also increase the compatibility between the liquid nitrile rubber and the alkali-soluble epoxy resin, and the obtained photosensitive resin composition and its photosensitive dry film can have high strength and toughness at the same time. DETAILED DESCRIPTION

[0085] The following embodiments are only some embodiments of the present invention, rather than all embodiments. Therefore, the detailed description in the embodiments of the present invention provided below is not intended to limit the scope of the present invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative work belong to the protection scope of the present invention.

[0086] In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in the industry. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

[0087] Production Example 1: Alkali-soluble photosensitive epoxy resin A1

[0088] 350 parts by mass of o-cresol epoxy resin (704, Shandong Shengquan Epoxy Resin, epoxy equivalent: 191.6), 70 parts by mass of acrylic acid, 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate are heated and stirred at 100°C to react and completely dissolve; 2 parts by mass of triphenylphosphine are added, and the heating reaction is continued at 100°C until the acid value no longer decreases; 98 parts by mass of tetrahydrophthalic anhydride and 85 parts by mass of carbitol acetate are added, and the reaction is carried out at 90°C for 6 hours; the mixture is cooled to room temperature and washed to obtain an alkali-soluble photosensitive o-cresol epoxy resin (alkali-soluble photosensitive epoxy resin A1, with an acid value of 78KOH / g).

[0089] Production Example 2: Alkali-soluble photosensitive epoxy resin A2

[0090] 350 parts by mass of bisphenol A (BPA) novolac epoxy resin (SQAN-203, Shandong Shengquan, epoxy equivalent: 173.31), 70 parts by mass of acrylic acid, 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate are heated and stirred at 100°C to react and completely dissolve; 2 parts by mass of triphenylphosphine are added, and the heating reaction is continued at 100°C until the acid value no longer decreases; 98 parts by mass of tetrahydrophthalic anhydride and 85 parts by mass of carbitol acetate are added, and the reaction is carried out at 90°C for 6 hours; the reaction is cooled to room temperature, and an alkali-soluble photosensitive bisphenol A novolac epoxy resin (alkali-soluble photosensitive epoxy resin A2, with an acid value of 85KOH / g) is obtained after washing.

[0091] Preparation Example 3: Alkali-soluble phosphorus-containing polyurethane acrylic resin C1

[0092] 150 parts by mass of polyether polyol C2040 (Wanhua Chemical), 150 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (HMDI), 180 parts by mass of lauryl methacrylate, 0.3 parts by mass of dibutyltin dilaurate, 0.3 parts by mass of hydroquinone and 20 parts by mass of hydroxyethyl acrylate were reacted at 90°C by introducing nitrogen gas to obtain polyurethane acrylate containing -NCO reactive groups;

[0093] 50 parts by weight of the above-mentioned polyurethane acrylate containing -NCO reactive groups were dissolved in 80 parts by weight of anhydrous polypropylene glycol. After the temperature was raised to 85° C., 20 parts by weight of triethylene glycol phosphate were added dropwise. The reaction was continued at 85° C. for 2 hours. During the reaction, samples were taken to test the -NCO content in the system. When the content was ≤0.2%, the reaction was stopped and an alkali-soluble phosphorus-containing polyurethane acrylate resin (C1) was separated.

[0094] -NCO content determination method: accurately weigh about 3g of sample into a clean conical flask, add 20mL of anhydrous toluene to dissolve the sample, add 10.0mL of 0.1mol / L di-n-butylamine-toluene solution (the former is the solute and the latter is the solvent) with a pipette, shake well, place at room temperature for 20-40min, add 40-50mL of isopropanol (or ethanol), use a few drops of bromocresol green as an indicator, and titrate with 0.5mol / L hydrochloric acid as a standard solution. When the solution changes from blue to yellow, it is the end point, and a blank test is performed.

[0095] -NCO content calculation formula: -NCO (%) = (V 1 -V 0 )c*0.042 / m×100%

[0096] Where:

[0097] V 0 The volume of the blank hydrochloric acid standard solution consumed (mL);

[0098] V 1 The volume of hydrochloric acid standard solution consumed by the sample (mL);

[0099] c is the concentration of the hydrochloric acid standard solution (mol / L);

[0100] m is the mass of the sample (g).

[0101] Preparation Example 4: Alkali-soluble phosphorus-containing polyurethane acrylic resin C2

[0102] 150 parts by mass of polyether polyol PCL 220 (Japan Daicel), 150 parts by mass of 4,4'-dicyclohexylmethane diisocyanate, 180 parts by mass of lauryl methacrylate, 0.3 parts by mass of dibutyltin dilaurate, 0.3 parts by mass of hydroquinone and 20 parts by mass of hydroxyethyl acrylate were reacted at 90°C by introducing nitrogen gas to obtain polyurethane acrylate containing -NCO reactive groups;

[0103] 50 parts by weight of the polyurethane acrylate containing -NCO reactive groups synthesized above were dissolved in 80 parts by weight of anhydrous polypropylene glycol. After heating to 85° C., 20 parts by weight of triethylene glycol phosphate were added dropwise. The reaction was continued at 85° C. for 2 hours. During the reaction, samples were taken to test the -NCO content in the system. When the content was ≤0.2%, the reaction was stopped and an alkali-soluble aliphatic phosphorus-containing polyurethane acrylate resin (C2) was separated.

[0104] Embodiment 1-4:

[0105] The photosensitive resin composition was prepared according to the mass fractions shown in Table 1:

[0106] Table 1

[0107]

[0108]

[0109] In the above table, SiO 2 The particle size is 0.3 μm.

[0110] Comparative Example 1-2:

[0111] The resin composition was prepared according to the mass fractions shown in Table 2:

[0112] Table 2

[0113]

[0114] In the above table, difunctional aliphatic polyurethane acrylate U-6282 was purchased from Covestro.

[0115] Effect embodiment 1:

[0116] The resin compositions in Examples 1-4 and Comparative Examples 1-2 were prepared into photosensitive dry films, which were coated on FCBGA substrates by thermal lamination. Specifically, acetone solvent was added to the photosensitive resin composition until the solid content was 58 wt %. After sufficient stirring and mixing, the mixture was evenly coated on a polyethylene terephthalate film using a coating machine, and dried in a dryer at 95° C. for 5 minutes. The photosensitive resin composition formed a 5 μm thick photosensitive dry film. Next, a cover film was attached to the surface of the photosensitive dry film to obtain a photosensitive resin laminate. The cover film of the photosensitive resin laminate was then peeled off and laminated on the FCBGA substrate using a hot roller laminating device (manufactured by Asahi Kasei Microdevices Corporation, AL-700) at a roller temperature of 105° C. The air pressure was set to 0.35 MPa and the lamination speed was set to 1.5 m / min. Performance tests were then conducted. The test methods and test results are shown in Table 3 below.

[0117] Table 3

[0118]

[0119]

[0120] As can be seen from Table 3, the photosensitive resin compositions prepared in Examples 1-4 of the present invention all have excellent electrical properties, mechanical properties, corrosion resistance and weather resistance: The difference between Comparative Example 1 and Examples 1-4 is that the polyurethane acrylate used in Comparative Example 1 is a phosphorus-free difunctional aliphatic polyurethane acrylate, and its performance is compared with that of Examples 1-4. While the solder resistance performance is reduced, the electrical performance, adhesion and elongation at break are all reduced. The difference between Comparative Example 2 and Examples 1-4 is that no alkali-soluble polyurethane acrylate is used, and its performance is compared with that of Examples 1-4. While the solder resistance performance is reduced, the adhesion, electrical properties, weather resistance and elongation at break are all significantly reduced. By comparing Examples 1-4 and Comparative Example 1-2, it can be obtained that the photosensitive resin composition provided by the present invention, the addition of alkali-soluble phosphorus-containing polyurethane acrylate can not only improve the solder resistance performance, but also improve the electrical performance, adhesion and elongation at break.

[0121] Embodiment 5-8:

[0122] The resin composition was prepared according to the mass fractions shown in Table 4:

[0123] Table 4

[0124]

[0125]

[0126] In the above table, bisphenol F novolac epoxy resin EXA-7376 was purchased from DIC Corporation; carboxyl-terminated liquid nitrile rubber flexible epoxy resin was purchased from Chengfeng Chemical; flexible epoxy resin Jef-0211 was purchased from Changshu Jiafa; the photoinitiator was 2,4-diethylthioxanthone (DETX, Nippon Kayaku); the thermosetting agent was melamine (Aladdin); the particle size of silicon dioxide was 0.3 μm (SFP20M, Denki Chemical Industry); and the leveling agent BYK361 was purchased from BYK, Germany.

[0127] Comparative Examples 3-5

[0128] The resin composition was prepared according to the mass fractions shown in Table 5:

[0129] Table 5

[0130]

[0131] In the above table, bisphenol F novolac epoxy resin EXA-7376 was purchased from DIC Corporation; carboxyl-terminated liquid nitrile rubber flexible epoxy resin was purchased from Chengfeng Chemical; flexible epoxy resin Jef-0211 was purchased from Changshu Jiafa; the photoinitiator was 2,4-diethylthioxanthone (DETX, Nippon Kayaku); the thermosetting agent was melamine (Aladdin); the particle size of silicon dioxide was 0.3 μm (SFP20M, Electric Chemical Industry); and the leveling agent BYK361 was purchased from BYK, Germany.

[0132] Effect embodiment 2:

[0133] The resin compositions in Examples 5-8 and Comparative Examples 3-5 were prepared into photosensitive dry films, which were coated on FCBGA substrates by heat lamination. The specific operation was as follows: solvent acetone was added to the photosensitive resin composition until the solid content was 58wt%, and after sufficient stirring and mixing, the mixture was evenly coated on a polyethylene terephthalate film using a coating machine, and dried in a dryer at 95°C for 5 minutes, so that the photosensitive resin composition formed a 5μm thick photosensitive dry film. Next, a cover film was attached to the surface of the photosensitive dry film to obtain a photosensitive resin laminate, and then the cover film of the photosensitive resin laminate was peeled off and laminated on the FCBGA substrate using a hot roller laminating device (manufactured by Asahi Kasei Microdevices Corporation, AL-700) at a roller temperature of 105°C, with the air pressure set to 0.35Mpa and the laminating speed set to 1.5m / min; and then a performance test was performed. The test method and test results are shown in Table 6 below.

[0134] Table 6

[0135]

[0136]

[0137] It can be seen from Table 6 that the resin compositions prepared in Examples 5-8 of the present invention can improve the toughness and elongation at break of the dry films of the resin compositions compared to Comparative Examples 3-5 by using the flexible epoxy resin and the carboxyl-terminated liquid nitrile rubber as composite toughening agents.

[0138] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A photosensitive resin composition, It is characterized in that include: (A) component: 15 to 30 parts of an alkali-soluble photosensitive epoxy resin having an acid value of 60 to 200 KOH / g; (B) component: 0 to 15 parts of a second epoxy resin; (C) component: 0 to 5 parts of alkali-soluble phosphorus-containing polyurethane acrylic resin, excluding 0; (D) component: 0 to 25 parts of toughening agent; (E) component: 0-2 parts of photoinitiator; (F) Component: 0-2 parts of thermal curing agent; (G) component: 10 to 70 parts of inorganic filler; (H) component: 10 to 35 parts of solvent; The preparation method of the alkali-soluble phosphorus-containing polyurethane acrylic resin comprises the following steps: (1) reacting polyester polyol or polyether polyol, isocyanate polymer, alcohol monomer with unsaturated double bonds having free radical polymerizability, (meth) alkyl acrylate monomer, catalyst and inhibitor to obtain alkali-soluble polyurethane acrylate; (2) reacting the obtained alkali-soluble polyurethane acrylate with a phosphoric acid compound in a solvent to obtain the alkali-soluble phosphorus-containing polyurethane acrylate; the phosphoric acid compound is selected from at least one of triethylene glycol phosphate, diphenylphosphoric acid, bis(4-methylphenyl)phosphoric acid, bis(3-methylphenyl)phosphoric acid, bis(4-methoxyphenyl)phosphoric acid, bis(4-trifluoromethyl-phenyl)phosphoric acid, bis(1-methylnaphthyl)phosphoric acid and bis(2-methylnaphthyl)phosphoric acid.

2. The photosensitive resin composition according to claim 1, It is characterized in that The photosensitive resin composition comprises: (A) component: 20 to 30 parts of an alkali-soluble photosensitive epoxy resin having an acid value of 60 to 200 KOH / g; (C) component: 3 to 5 parts of alkali-soluble phosphorus-containing polyurethane acrylic resin; (F) Component: 0-2 parts of thermal curing agent; (G) component: 35-70 parts of inorganic filler; (H) Component: 25 to 35 parts of solvent.

3. The photosensitive resin composition according to claim 2, It is characterized in that The mass ratio of the (A) component to the (C) component is 1:0.1-10.

4. The photosensitive resin composition according to claim 1, It is characterized in that The photosensitive resin composition comprises: (A) component: 20 to 30 parts of an alkali-soluble photosensitive epoxy resin having an acid value of 60 to 200 KOH / g; (B) component: 5 to 15 parts of the second epoxy resin; (D) component: 10 to 25 parts of toughening agent; (E) component: 0-2 parts of photoinitiator; (F) Component: 0-2 parts of thermal curing agent; (G) component: 35-70 parts of inorganic filler; (H) Component: 25 to 35 parts of solvent.

5. The photosensitive resin composition according to claim 1, It is characterized in that The alkali-soluble photosensitive epoxy resin is an epoxy resin containing a photosensitive group and an alkali-soluble group on the molecular chain; the photosensitive group is a carbon-carbon double bond; and the alkali-soluble group is selected from at least one of a carboxyl group and an acid anhydride.

6. The photosensitive resin composition according to claim 5, It is characterized in that The alkali-soluble photosensitive epoxy resin is a phenolic epoxy resin modified by an organic acid containing a carbon-carbon double bond or an acid anhydride containing a carbon-carbon double bond.

7. The photosensitive resin composition according to claim 5, It is characterized in that The weight average molecular weight M of the alkali-soluble photosensitive epoxy resin w =5000~50000g / mol.

8. The photosensitive resin composition according to claim 1, It is characterized in that In step (1), the reaction temperature is 70-120°C.

9. The photosensitive resin composition according to claim 1, It is characterized in that In step (2), the reaction temperature is 70-100°C.

10. The photosensitive resin composition according to claim 1, It is characterized in that In step (2), the reaction is carried out until the content of -NCO in the reaction system is ≤0.2%.

11. The photosensitive resin composition according to claim 1, It is characterized in that The toughening agent is selected from at least one of carboxyl-terminated liquid nitrile rubber, flexible epoxy resin and hydroxyl-terminated polydimethylsiloxane.

12. The photosensitive resin composition according to claim 11, It is characterized in that The toughening agent is at least two of carboxyl-terminated liquid nitrile rubber, flexible epoxy resin and hydroxyl-terminated polydimethylsiloxane.

13. The photosensitive resin composition according to claim 11, It is characterized in that The flexible epoxy resin is an epoxy resin containing flexible segments or groups on the molecular chain; the flexible segments or groups are selected from at least one of sulfone groups, thioether bonds, methyl groups, carbonyl groups and trifluoromethyl groups.

14. The photosensitive resin composition according to claim 1, It is characterized in that The inorganic filler is selected from silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), Tantalum Oxide (Ta 2 O 5 )、ZrO 2 ), silicon nitride (Si 3 N 4 ), barium titanate (BaO·TiO 2 ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga 2 O 3 )、spinel (MgO·Al 2 O 3 ), mullite (3Al 2 O 3 ·2SiO 2 )、cordierite (2MgO·2Al 2 O 3 / 5SiO 2 )、Talc(3MgO·4SiO 2 ·H 2 O), aluminum titanate (TiO 2 ·Al 2 O 3 ), yttria-containing zirconium oxide (Y 2 O 3 ·ZrO 2 ), barium silicate (BaO·8SiO 2 ), boron nitride (BN), calcium carbonate (CaCO 3 ), barium sulfate (BaSO 4 ), calcium sulfate (CaSO 4 ), at least one of hydrotalcite, mica, carbon (C), bentonite and montmorillonite.

15. The photosensitive resin composition according to claim 1, It is characterized in that The particle size of the inorganic filler is 0.1 to 20 μm.

16. The photosensitive resin composition according to claim 15, It is characterized in that The particle size of the inorganic filler is 0.1 to 10 μm.

17. The photosensitive resin composition according to claim 16, It is characterized in that The particle size of the inorganic filler is 0.1 to 5 μm.

18. The photosensitive resin composition according to claim 17, It is characterized in that The particle size of the inorganic filler is 0.1-1 μm.

19. The photosensitive resin composition according to claim 1, It is characterized in that The solvent is selected from at least one of alcohols, glycol ethers and esters.

20. The photosensitive resin composition according to claim 1, It is characterized in that The invention also comprises component (I): an auxiliary agent; the auxiliary agent comprises at least one of a pigment, a leveling agent and a defoaming agent.

21. A photosensitive film prepared from the photosensitive resin composition according to any one of claims 1 to 20, It is characterized in that The photosensitive film is obtained by curing a solution comprising the photosensitive resin composition.

22. The photosensitive film according to claim 21, It is characterized in that The thickness of the photosensitive film is 5 to 200 μm.

23. The photosensitive film according to claim 21, It is characterized in that The thickness of the photosensitive film is 15-60 μm.

24. The photosensitive film according to claim 21, It is characterized in that The thickness of the photosensitive film is 20-50 μm.

25. The photosensitive film according to claim 21, It is characterized in that The solvent in the solution including the photosensitive resin composition is selected from at least one of acetone and carbitol acetate.

26. The photosensitive film according to claim 21, It is characterized in that The curing is thermal curing; the thermal curing condition is 80-130° C. for 3-10 minutes.

27. Use of the photosensitive resin composition according to any one of claims 1 to 20 in the field of electronic packaging, It is characterized in that Application in the preparation of photoresists.

28. A photosensitive resin laminate, It is characterized in that The invention comprises a support and the photosensitive film according to claim 21 disposed on the support.

29. The photosensitive resin laminate according to claim 28, It is characterized in that A protective film is arranged on the photosensitive film.

Images