阅读说明：本技术 一种低卤低硫感光阻焊材料及其制备方法 (A kind of low-halogen low sulphur photosensitive solder resist material and preparation method thereof ) 是由 钟远波 周瑞波 李光星 于 2019-08-08 设计创作，主要内容包括：本发明提供了一种低卤低硫感光阻焊材料,按重量份数计,包括以下原料组分：感光树脂30-45份,低卤环氧树脂10-25份,填料20-45份,助剂1-8份,溶剂5-10份,光引发剂2-8份,感光单体1-10份,其中所述低卤环氧树脂为低卤双酚A环氧树脂、低卤酚醛环氧树脂、低卤甲酚环氧树脂中的至少一种,所述低卤环氧树脂中卤素含量不超过900ppm；所述低卤低硫感光阻焊材料的硫含量低于500ppm。本发明的低卤低硫感光阻焊材料可以有效改善PCB化学银表面处理工艺银变色以及LED照明镀银电子零件脚或者镀银银镜反射面发黑的问题,卤素、硫含量满足国际和行业标准。(The present invention provides a kind of low-halogen low sulphur photosensitive solder resist materials, according to parts by weight, including following raw material components: 30-45 parts of photosensitive resin, 10-25 parts of low halogen epoxy resin, 20-45 parts of filler, 1-8 parts of auxiliary agent, 5-10 parts of solvent, 2-8 parts of photoinitiator, 1-10 parts of photoactive, wherein the low halogen epoxy resin is at least one of low halogen bisphenol A epoxide resin, low halophenol formaldehyde epoxy resin, low halogen cresol epoxy resin, and content of halogen is no more than 900ppm in the low halogen epoxy resin；The sulfur content of the low-halogen low sulphur photosensitive solder resist material is lower than 500ppm.Low-halogen low sulphur photosensitive solder resist material of the invention can be effectively improved the problem of PCB chemistry silver surface treatment process silver tarnish and the silver-plated electronic component foot of LED illumination or silver-plated silver mirror reflecting surface nigrescence, and halogen, sulfur content meet international and professional standard.)

1. a kind of low-halogen low sulphur photosensitive solder resist material, which is characterized in that according to parts by weight, including following raw material components:

Wherein the low halogen epoxy resin is low halogen bisphenol A epoxide resin, low halophenol formaldehyde epoxy resin, low halogen cresol epoxy resin At least one of, content of halogen is no more than 900ppm in the low halogen epoxy resin；The low-halogen low sulphur photosensitive solder resist material Sulfur content be lower than 500ppm.

2. low-halogen low sulphur photosensitive solder resist material according to claim 1, which is characterized in that the photosensitive resin is by with lower section Method preparation: in the reaction vessel, by 8-15 parts of acrylic acid, 30-45 parts of low halogen epoxy resin, 35-45 parts of dibasic ester, triphenyl 0.2-0.8 parts of phosphorus, 0.2-0.6 parts of hydroquinone be heated to 100-110 DEG C of reaction 8-12 hours after, add 10-15 parts of acid anhydrides, Reaction 4-6 hours.

3. low-halogen low sulphur photosensitive solder resist material according to claim 1, which is characterized in that the acid value of the photosensitive resin is 45-65mgKOH/g, solid content 55-65%.

4. low-halogen low sulphur photosensitive solder resist material according to claim 1, which is characterized in that the solvent is ether solvent And/or esters solvent.

5. low-halogen low sulphur photosensitive solder resist material according to claim 4, which is characterized in that the ether solvent includes the third two At least one of alcohol methyl ether, propandiol butyl ether, ethylene glycol ethyl ether, butyl glycol ether；The esters solvent include ethyl acetate, At least one of butyl acetate, isopropyl acetate.

6. low-halogen low sulphur photosensitive solder resist material according to claim 1, which is characterized in that the photoactive is three hydroxyl first Base propane triacrylate, ethoxylated trimethylolpropane triacrylate, isobornyl acrylate, dipentaerythritol 5 third At least one of olefin(e) acid ester, double pentaerythritol methacrylate.

7. low-halogen low sulphur photosensitive solder resist material according to claim 1, which is characterized in that the photoinitiator is 1- (connection Phenyl -4- base) -2- methyl -2- morpholinopropane -1- ketone, (2,4,6- tri-methyl chloride) diphenyl phosphine oxide, 4- diformazan At least one of base benzocaine.

8. low-halogen low sulphur photosensitive solder resist material according to claim 1, which is characterized in that the filler be silicon powder and/ Or talcum powder.

9. a kind of preparation method of low-halogen low sulphur photosensitive solder resist material according to claim 1 to 8, feature It is, is obtained after each raw material is mixed, disperses, grinds and filtered by weight.

10. a kind of low-halogen low sulphur photosensitive solder resist material according to claim 1 to 8 is applied to the method for PCB, Characterized by comprising the following steps:

(1) the low-halogen low sulphur photosensitive solder resist material is diluted to viscosity 90-180dPa.s with dibasic ester, republished in PCB Surface；

(2) by the PCB printed in 75-80 DEG C of dry 30-45min；

(3) dried PCB is exposed processing, then development obtains required figure；

(4) PCB to have developed is toasted at 140-160 DEG C.

Technical field

The invention belongs to solder resist material fields, and in particular to a kind of low-halogen low sulphur photosensitive solder resist material and preparation method thereof.

Background technique

Solder mask is the protective layer coated in printing board surface, it selectively protects printing board surface, the table of wiring board In addition to copper dish, other parts plate face is both needed to one layer of solder resist material of covering as permanent protection coating, to prevent scolding tin from making contact in face Cause short circuit, while excellent electric property, chemical resistance, moistureproof and mildewproof performance and the physical machine that solder resist material has Tool performance, also ensure wiring board in transport, storage, using upper safety and electrical property invariance.Therefore, welding resistance film quality Quality not only influence the appearance of printed board, but also will affect the service life of printed board.The master of existing white solder resist material Body resin composition be modified epoxy resin system, usually exist two major defects, first, epoxy resin be industrially apply most For extensive oligomer raw material, by the way that photopolymerization reaction occurs after photoinitiator is added, volume can serious receipts after photopolymerization It contracts, more crisp after material solidification, flexible poor, the easy embrittlement of hot setting；Second, material is crossing 220-260 DEG C of Reflow Soldering/3-5 When minute, because resin high temperature resistance is inadequate, lead to material under high temperature xanthochromia.

Solder mask is after processing is completed, it is necessary to reach the requirements such as adhesive force is strong, hardness is high, solvent resistant, acid and alkali-resistance, heat resistant oils. Since technical process is complex, not only select solder resist material extremely important, but also strict technology control in process of production System is more to ensure that the key point of solder mask quality.

Summary of the invention

In view of the problems of the existing technology, one of the objects of the present invention is to provide a kind of low-halogen low sulphur photosensitive solder resist materials Material can meet the non-discolouring requirement of light shine in illuminating line plate market in aspect of performance, and be effectively improved PCB chemistry silver The problem of process of surface treatment silver tarnish and the silver-plated electronic component foot of LED illumination or silver-plated silver mirror reflecting surface black；This hair Bright another object is to provide the preparation method of low-halogen low sulphur photosensitive solder resist material；It is yet another object of the invention to provide low-halogen lows The application method of sulphur photosensitive solder resist material.

In order to overcome the shortcomings of the prior art, low-halogen low sulphur photosensitive solder resist material of the invention, passes through following technology Scheme is realized:

A kind of low-halogen low sulphur photosensitive solder resist material, according to parts by weight, including following raw material components:

Wherein the low halogen epoxy resin is low halogen bisphenol A epoxide resin, low halophenol formaldehyde epoxy resin, low halogen cresol epoxy At least one of resin, content of halogen is no more than 900ppm, preferably more than 750ppm in the low halogen epoxy resin, more excellent Choosing is no more than such as 500ppm, 450ppm, 400ppm, 350ppm.

Further, in the low halogen epoxy resin content of halogen be no more than 300ppm, such as 300ppm, 250ppm, 200ppm、150ppm。

Further, in the low halogen epoxy resin content of halogen be no more than 100ppm, such as 100ppm, 80ppm, 60ppm、50ppm、40ppm、30ppm、20ppm。

It is highly preferred that being halogen-free in the low halogen epoxy resin.

Further, content of halogen is no more than 900ppm in the low-halogen low sulphur photosensitive solder resist material, preferably more than 750ppm, more preferably no more than such as 500ppm, 450ppm, 400ppm, 350ppm.

Further, in the low-halogen low sulphur photosensitive solder resist material content of halogen be no more than 300ppm, such as 300ppm, 250ppm、200ppm、150ppm。

Further, in the low-halogen low sulphur photosensitive solder resist material content of halogen be no more than 100ppm, such as 100ppm, 80ppm、60ppm、50ppm、40ppm、30ppm、20ppm。

It is highly preferred that being halogen-free in the low-halogen low sulphur photosensitive solder resist material.

For example, the sulfur content of the low-halogen low sulphur photosensitive solder resist material be lower than 500ppm, such as less than 450ppm, 400ppm、350ppm、300ppm、250ppm、200ppm、150ppm、100ppm、80ppm、60ppm、50ppm、40ppm、 30ppm、20ppm。

Further, the low-halogen low sulphur photosensitive solder resist material is free of S (sulphur).

For example, the low-halogen low sulphur photosensitive solder resist material not containing sulfate, such as barium sulfate.

The S of the low-halogen low sulphur photosensitive solder resist material is detected by HeLeeX E8 SPR elemental analyser (1.1S model) (sulphur) content, fluorescence intensity is 0.00 as the result is shown, i.e., the described low-halogen low sulphur photosensitive solder resist material is free of S (sulphur).

Further, the photosensitive resin is prepared by following methods: in the reaction vessel, by 8-15 parts of acrylic acid, low halogen (the low halogen epoxy resin is low halogen bisphenol A epoxide resin, low halophenol formaldehyde epoxy resin, low halogen cresol epoxy resin to epoxy resin At least one of, wherein content of halogen is no more than 500ppm) 30-45 parts, 35-45 parts of dibasic ester, triphenyl phosphorus 0.2-0.8 Part, 0.2-0.6 part of hydroquinone be heated to 100-110 DEG C of reaction 8-12 hours after, add 10-15 parts of acid anhydrides, it is small to react 4-6 When (such as reaction temperature be 105 DEG C).

Further, the acid anhydrides includes one of the third acid anhydride of tetrahydro, the third acid anhydride of hexahydro, maleic anhydride or a variety of.

Further, the acid value of the photosensitive resin is 45-65mgKOH/g (preferably 55-65mgKOH/g), and solid content is 55-65%.

Further, the solvent is ether solvent and/or esters solvent.

Further, the ether solvent includes propylene glycol monomethyl ether, propandiol butyl ether, ethylene glycol ethyl ether, butyl glycol ether At least one of；The esters solvent includes at least one of ethyl acetate, butyl acetate, isopropyl acetate.

Further, the photoactive is trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane three Acrylate, isobornyl acrylate, double pentaerythritol C5 methacrylate, at least one in double pentaerythritol methacrylate Kind.

Further, the photoinitiator be 1- (xenyl -4- base) -2- methyl -2- morpholinopropane -1- ketone, (2,4, 6- tri-methyl chloride) diphenyl phosphine oxide, at least one of ethyl 4-dimethylaminobenzoate.

Further, the filler is silicon powder and/or talcum powder.Optionally, the filler is silica.

Further, the filler is free of S (sulphur).

For example, the filler not containing sulfate, such as barium sulfate.

A kind of preparation method of low-halogen low sulphur photosensitive solder resist material, each raw material is mixed by weight, is dispersed, is ground and mistake It is obtained after filter.

Preferably, by photosensitive resin, low halogen epoxy resin, filler, auxiliary agent, solvent and photoactive, photoinitiator by weight Part is measured to weigh, after high speed dispersion is uniform on dispersion machine, in being ground to fineness≤20 μm on three-roller, preferably≤10 μm ,≤5 μ M refilters and removes mechanical admixture and coarse grain, finished-product material is made.

A kind of low-halogen low sulphur photosensitive solder resist material is applied to the method for PCB, comprising the following steps:

(1) the low-halogen low sulphur photosensitive solder resist material is diluted to viscosity 90-180dPa.s with dibasic ester, republished PCB surface；

(2) by the PCB printed in 75-80 DEG C of dry 30-45min；

(3) dried PCB is exposed processing, then development obtains required figure；

(4) PCB to have developed is dried at 140-160 DEG C (such as 150 DEG C).

Compared with the existing technology, beneficial effects of the present invention:

Low-halogen low sulphur photosensitive solder resist material of the invention can meet the prolonged constant of illumination market in aspect of performance Color is effectively improved PCB chemistry silver surface treatment process silver tarnish and the silver-plated electronic component foot of LED illumination or silver-plated silver mirror The problem of reflecting surface blacks, halogen meets the low halogen standard in the whole world, in addition, comprehensive performance is very excellent, hence it is evident that it is better than similar product, Especially resistance to acid and alkali, insulated electro be resistive, wet-heat resisting, cold-and-heat resistent impact etc. is very prominent.

Specific embodiment

In order to preferably explain the present invention, it is described further now in conjunction with following specific embodiments, but the present invention is unlimited In specific embodiment.