CN1040602A - A kind of preparation method of photocuring etchingresistant printing material - Google Patents
A kind of preparation method of photocuring etchingresistant printing material Download PDFInfo
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- CN1040602A CN1040602A CN 88105564 CN88105564A CN1040602A CN 1040602 A CN1040602 A CN 1040602A CN 88105564 CN88105564 CN 88105564 CN 88105564 A CN88105564 A CN 88105564A CN 1040602 A CN1040602 A CN 1040602A
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- resin
- seal material
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Abstract
The invention belongs to the silk screen process seal material that the printed circuit board manufacturing process adopts.The invention provides a kind of photosensitivity and hardness and improve, can improve laser curing velocity, the viscosity variation varies with temperature not greatly different, the preparation method of the photocuring etchingresistant printing material of striping excellent property.Principal character is: photoresist also adopts modified phosphate resin and modified epoxy-acrylic acid series water soluble resin in the prescription except that adopting modified tung oil resin, modification half fat resin, modified rosin resin.The etchingresistant printing material that the inventive method makes has that caustic solubility is good, advantages such as curing speed is fast, the low printing performance of viscosity and good stability.
Description
The invention belongs to the silk screen process seal material that the printed circuit board manufacturing process adopts.
Photocuring etchingresistant printing material generally is made up of photoresist, photoinitiator, filler, hot stopper, defoamer etc., and through certain proportioning combination, mechanical rolling forms.As the clear 58-49711 report of foreign patent day disclosure special permission communique.Photoresist adopts modified tung oil resin, modification half ester resin, modified rosin resin, and does not see and adopt modified phosphate resin, modified epoxy.Though domestic had a report: Resins, epoxy can be used on the printed circuit board, form epoxy-acrylic acid series water soluble resin through modification and be used for the seal material and still be not reported.
The object of the present invention is to provide a kind of photosensitivity and hardness to improve, can improve laser curing velocity, the viscosity variation varies with temperature not greatly different, the preparation method of the photocuring etchingresistant printing material of striping excellent property.Adopt modified epoxy-acrylic acid series water soluble resin in the photoresist, can improve photosensitivity, hardness and the raising laser curing velocity of seal material; Adopt modified phosphate can improve the photosensitivity and the striping of seal material.
The inventive method is:
1, various components and proportioning thereof are:
| Component | Weight ratio % | Component | Weight ratio % |
| The sensitization alkali soluble resins | 80－50 | Mould inhibitor | 0.5-0.1 |
| Reactive thinner | 15－12 | Hot stopper | 0.5-0.3 |
| Photoinitiator | 10－2 | Lubricant | 0.5-0.1 |
| Thixotropic agent | 2－1 | Adhesion promoter | 0.6-0.04 |
| Weighting agent | 27-3 |
2, (down together) sensitization alkali soluble resins is selected molecular weight 200～2000 for use, the acrylic resin of an above photosensitivity group is arranged in table 1 component, and acid number is at 30～300KOHmg/g.The general formula of resin is expressed as
R in the formula
1Be H or alkyl;
R
2Be alkylidene;
R
3For
Group or vinyl.
Main five classes that adopt:
(1) the tung oil resin (TM) of maleic anhydride modified
By cis-butenedioic anhydride and tung oil reaction, reactant reacts with the senecioate hydroxyalkyl again, as propenoic acid beta-hydroxy ethyl ester earlier.
Reaction formula: (a)
In the formula: G is a glyceryl
ROH is a propenoic acid beta-hydroxy alkane ester, as propenoic acid beta-hydroxy ethyl ester.
(2) modified phosphate class: di(2-ethylhexyl)phosphate propenoic acid beta-hydroxy alkane ester, as di(2-ethylhexyl)phosphate propenoic acid beta-hydroxy ethyl (HEAP) by P
2O
5With the reaction of senecioate hydroxyl ethyl ester, reaction formula
(3) modified epoxy class: the affixture of epoxy-vinylformic acid and MALEIC ANHYDRIDE (EAM).By Resins, epoxy and vinylformic acid reaction, reactant reacts with cis-butenedioic anhydride more earlier.
(4) modified rosin resin (RM)
By Gum Rosin and cis-butenedioic anhydride reaction, reactant reacts with propenoic acid beta-hydroxy alkane ester more earlier.As the propenoic acid beta-hydroxy propyl ester.
Reaction formula: (a)
(5) modification half fat resin:
The compound (THEA) of Tetra hydro Phthalic anhydride and senecioate hydroxyl ethyl ester
The compound of Tetra hydro Phthalic anhydride and senecioate hydroxypropyl acrylate (THPA)
Reaction formula is:
The compound (MHEA) of MALEIC ANHYDRIDE and senecioate hydroxyl ethyl ester
The compound of MALEIC ANHYDRIDE and senecioate hydroxypropyl acrylate (MHPA)
Reaction formula:
The senecioate hydroxyl second propyl ester affixture (SMHEA) of phenylethylene-maleic anhydride interpolymer
3, reactive thinner:
The photosensitivity reactive thinner plays letdown resin and adds the effect of print duplication material solidified.Various esters of acrylic acids commonly used.
(1) Viscoat 295 (TMPTA)
(RO-CH
2)
3-C-CH
2CH
3, R is an acryl
(2) the triethylene glycol double methacrylate (PEGDA) that contracts more
RO[-CH
2CH
2O-]
n-CH
2CH
2-OR, R are acryl
(3) phthalic acid double propenyl ester (DPA)
(4) senecioate hydroxyl ethyl ester (HEA)
(5) senecioate hydroxypropyl acrylate (HPA)
(6) methacrylic acid-β hydroxyl ethyl ester (HEMA)
(7) methacrylic acid-β hydroxypropyl acrylate (HPMA)
4, photoinitiator:
(1) st-yrax class, as
The peace ether
The peace isopropyl ether
The peace butyl ether
The peace ethyl isobutyl ether
(2) anthraquinone class: alkyl-anthraquinone, as:
Tectoquinone
EAQ
The propyl group anthraquinone
The tertiary butyl anthraquinone
(3) benzophenone, as:
Benzophenone
Miaow ketone
5, thixotropic agent, as:
Aerosil
Wilkinite
Diatomite
6, mould inhibitor: as Viola crystallina, methyl violet etc.
7, hot stopper: phenols or diphenols.As alkoxy phenol, Resorcinol.
8, lubricant: as methyl-silicone oil, higher fatty acid metallic salt.
9, adhesion promoter: imidazoles, as benzotriazole, Methylimidazole.
10, weighting agent: titanium dioxide.
11, preparation technology:
By above-listed component proportioning, the order batching (mixed, after three-roller rolling and levigate reaches certain fineness (quality index is 5 μ) packing in normal temperature, normal pressure, stirring in 50～1000rPM) 0.5～4 hours successively.
The seal material that the inventive method makes has that caustic solubility is good, and curing speed is fast, and viscosity is lower, advantages such as printing performance and good stability, and this seal material flash-point is higher, belongs to non-dangerous goods, no three wastes generation in the production.The salient features of this seal material has reached Japanese Western Japan Trading Co.,Ltd and Italian Argon(Argonne) technical indicator of company's like product.Low price half, it can substituting import one the seal material, for country saves a large amount of foreign exchanges.The sensitization condition of cure: three of high voltage mercury lamp 80w/cm, lamp are apart from 10cm, and curing speed is 3～6 meters; One of high voltage mercury lamp 80w/cm, lamp be apart from 10cm, set time＜45 second.Etch resistant properties: corrosion-resistant, acid etching solutions such as the iron trichloride of ability 15% concentration, cupric chloride, ammonium persulphate, hydrogen peroxide; Anti-plating, ability acid copper-plating, terne coating.
Embodiment 1,
Various components and proportioning
Component weight ratio %
Photoresist; Modified tung oil 8.39
Phthalic anhydride-β hydroxyl ethyl ester 49.92
Reactive thinner: Viscoat 295 7.55
Triethylene glycolbismethyl-acrylate 5.45
Photoinitiator; EAQ 2.68
Benzophenone 0.42
Thixotropic agent: aerosil 1.51
Mould inhibitor: methyl violet 0.34
Hot stopper: Resorcinol 0.34
Lubricant: methyl-silicone oil 0.34
Adhesion promoter: benzotriazole 0.08
Weighting agent: talcum powder 22.98
Batching (mixed, and after three-roller rolls with levigate, reached certain fineness (quality index is 5 μ) packing in normal temperature, normal pressure, stirring in 50～1000rPM) 2 hours successively.
Embodiment 2-
Various components and proportioning:
Component weight ratio %
Photoresist; Rosin tree fatty oil 20
Phthalic anhydride-β hydroxyl ethyl ester 15
Phthalic anhydride-β hydroxypropyl acrylate 17
Reactive thinner: Viscoat 295 7
Triethylene glycolbismethyl-acrylate 6
Senecioate hydroxyl ethyl ester 2.56
Photoinitiator; EAQ 3.2
Benzophenone 0.5
Thixotropic agent: aerosil 1.2
Mould inhibitor: methyl violet 0.34
Hot stopper: Resorcinol 0.4
Lubricant: methyl-silicone oil 0.4
Adhesion promoter: benzotriazole 0.2
Weighting agent: talcum powder 26.2
Preparation process condition is with embodiment 1
Embodiment 3:
Various components and proportioning:
Component weight ratio %
Photoresist; Modified epoxy vinylformic acid water soluble resin 20
Phthalic anhydride-β hydroxyl ethyl ester 15
Phthalic anhydride-β hydroxypropyl acrylate 17
Reactive thinner: Viscoat 295 7.7
Triethylene glycolbismethyl-acrylate 7.5
Senecioate hydroxyl ethyl ester 0.5
Photoinitiator; Benzoin isobutyl ether 4
Thixotropic agent: aerosil 1.2
Mould inhibitor: methyl violet 0.4
Hot stopper: Resorcinol 0.4
Lubricant: methyl-silicone oil 0.4
Adhesion promoter: benzotriazole 0.2
Weighting agent: talcum powder 25.7
Preparation process condition: with embodiment 1.
Claims (10)
1, a kind of photocuring etchingresistant printing material of being made up of photoresist, photoinitiator, filler etc. the invention is characterized in that photoresist can adopt modified phosphate, modified epoxy-vinylformic acid water soluble resin, and various components and prescription thereof are:
The batching back is stirred under normal temperature, normal pressure and was mixed in 0.5-4 hour, after three-roller roll extrusion and levigate reaches certain fineness packing.
2, seal material formula as claimed in claim 1 is characterized by the acrylic resin that used photoresist is selected molecular weight 200-2000 for use, an above photosensitivity group is arranged, and acid number is at 30-300mgKOH/g, and the general formula of resin is expressed as:
R in the formula
1Be H or alkyl,
R
2Be alkylidene,
R
3For and group or vinyl,
Main five classes that adopt:
1. the tung oil resin of maleic anhydride modified;
2. modified phosphate lipid is as di(2-ethylhexyl)phosphate propenoic acid beta hydroxyl ethyl ester;
3. modified epoxy class is as the affixture of epoxy-vinylformic acid and MALEIC ANHYDRIDE;
4. modified rosin resin is as rosin-cis-butenedioic anhydride-propenoic acid beta hydroxypropyl acrylate affixture;
5. modification half fat resin.As phthalic anhydride-propenoic acid beta hydroxyl second (third) ester or cis-butenedioic anhydride-propenoic acid beta hydroxyl second (third) ester or vinylbenzene-cis-butenedioic anhydride-propenoic acid beta hydroxyl ethyl ester affixture.
3, seal material formula as claimed in claim 1, it is characterized by used reactive thinner is following esters of acrylic acid:
1. Viscoat 295;
2. the triethylene glycol double methacrylates that contract more;
3. phthalic acid double propenyl ester;
4. propenoic acid beta hydroxyl ethyl ester;
5. propenoic acid beta hydroxypropyl acrylate;
6. methacrylic acid β hydroxyl ethyl ester;
7. methacrylic acid β hydroxypropyl acrylate;
4, seal material formula as claimed in claim 1 is characterized by used photoinitiator and is:
1. st-yrax class is as peace ether, peace isopropyl ether, peace butyl ether, peace ethyl isobutyl ether;
2. anthraquinone class is as alkyl-anthraquinone: tectoquinone, EAQ, propyl group anthraquinone, tertiary butyl anthraquinone;
3. benzophenone is as benzophenone, miaow ketone.
5, seal material formula as claimed in claim 1, it is characterized by used thixotropic agent is aerosil or wilkinite or diatomite.
6, seal material formula as claimed in claim 1, it is characterized by used mould inhibitor is Viola crystallina or methyl violet.
7, seal material formula as claimed in claim 1, it is characterized by used hot stopper is phenols or diphenols, the piperazine class is as alkoxy phenol, Resorcinol.
8, seal material formula as claimed in claim 1, it is characterized by used lubricant is methyl-silicone oil or senior ester fat acid metal salt class.
9, seal material formula as claimed in claim 1, it is characterized by used adhesion promoter is imidazoles, as benzotriazole, Methylimidazole.
10, seal material formula as claimed in claim 1, it is characterized by used weighting agent is titanium dioxide, talcum powder, silicon-dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105564 CN1028373C (en) | 1988-08-25 | 1988-08-25 | Method of producing photocuring etchingresistant printing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105564 CN1028373C (en) | 1988-08-25 | 1988-08-25 | Method of producing photocuring etchingresistant printing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040602A true CN1040602A (en) | 1990-03-21 |
| CN1028373C CN1028373C (en) | 1995-05-10 |
Family
ID=4833744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105564 Expired - Fee Related CN1028373C (en) | 1988-08-25 | 1988-08-25 | Method of producing photocuring etchingresistant printing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1028373C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000037453A1 (en) * | 1998-12-22 | 2000-06-29 | Qinetiq Limited | Photoactive propane derivatives and orientation layers |
| CN100374293C (en) * | 2001-04-10 | 2008-03-12 | 拜尔公司 | Heat-absorbing layer system |
| CN101448862B (en) * | 2006-06-02 | 2011-12-14 | 昭和电工株式会社 | Photosensitive resin and photosensitive resin composition |
| CN102295856A (en) * | 2010-06-25 | 2011-12-28 | 深圳市顾康力化工有限公司 | Aqueous UV (ultraviolet) solidified silk screen ink and manufacturing process thereof |
| CN102391123A (en) * | 2011-08-31 | 2012-03-28 | 河南金誉包装科技股份有限公司 | Light-cured tetrahydrophthalic anhydridized tung oil acrylate resin and preparation method thereof |
| CN104559473A (en) * | 2015-01-30 | 2015-04-29 | 河源诚展科技有限公司 | Water-based screen printing electroplating-resistant etching-resistant ink |
| CN106752175A (en) * | 2016-11-13 | 2017-05-31 | 惠州市大亚湾科翔科技电路板有限公司 | A kind of wiring board cured film and printed wiring board |
| CN110845909A (en) * | 2019-11-21 | 2020-02-28 | 珠海宏博电子科技有限公司 | Photosensitive solder resist white oil and preparation method thereof |
| CN114836757A (en) * | 2022-04-22 | 2022-08-02 | 北京柏盛名匠标识制作有限公司 | Metal label manufacturing method based on etching process |
-
1988
- 1988-08-25 CN CN 88105564 patent/CN1028373C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000037453A1 (en) * | 1998-12-22 | 2000-06-29 | Qinetiq Limited | Photoactive propane derivatives and orientation layers |
| US6653499B1 (en) | 1998-12-22 | 2003-11-25 | Qinetiq Limited | Photoactive propane derivatives and orientation layers |
| CN100374293C (en) * | 2001-04-10 | 2008-03-12 | 拜尔公司 | Heat-absorbing layer system |
| CN101448862B (en) * | 2006-06-02 | 2011-12-14 | 昭和电工株式会社 | Photosensitive resin and photosensitive resin composition |
| CN102295856A (en) * | 2010-06-25 | 2011-12-28 | 深圳市顾康力化工有限公司 | Aqueous UV (ultraviolet) solidified silk screen ink and manufacturing process thereof |
| CN102295856B (en) * | 2010-06-25 | 2014-01-01 | 深圳市顾康力化工有限公司 | Aqueous UV (ultraviolet) solidified silk screen ink and manufacturing process thereof |
| CN102391123A (en) * | 2011-08-31 | 2012-03-28 | 河南金誉包装科技股份有限公司 | Light-cured tetrahydrophthalic anhydridized tung oil acrylate resin and preparation method thereof |
| CN102391123B (en) * | 2011-08-31 | 2013-04-17 | 河南金誉包装科技股份有限公司 | Preparation method of light-cured tetrahydrophthalic anhydridized tung oil acrylate resin |
| CN104559473A (en) * | 2015-01-30 | 2015-04-29 | 河源诚展科技有限公司 | Water-based screen printing electroplating-resistant etching-resistant ink |
| CN106752175A (en) * | 2016-11-13 | 2017-05-31 | 惠州市大亚湾科翔科技电路板有限公司 | A kind of wiring board cured film and printed wiring board |
| CN110845909A (en) * | 2019-11-21 | 2020-02-28 | 珠海宏博电子科技有限公司 | Photosensitive solder resist white oil and preparation method thereof |
| CN114836757A (en) * | 2022-04-22 | 2022-08-02 | 北京柏盛名匠标识制作有限公司 | Metal label manufacturing method based on etching process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1028373C (en) | 1995-05-10 |
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