CN103901722A - Alkaline imaging photosensitive resin composition and preparation method thereof - Google Patents
Alkaline imaging photosensitive resin composition and preparation method thereof Download PDFInfo
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- CN103901722A CN103901722A CN201410173460.4A CN201410173460A CN103901722A CN 103901722 A CN103901722 A CN 103901722A CN 201410173460 A CN201410173460 A CN 201410173460A CN 103901722 A CN103901722 A CN 103901722A
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Abstract
The invention relates to an alkaline imaging photosensitive resin composition which is characterized by comprising the following components in parts by weight: (1) 20-35 parts of quick-drying type carboxyl-containing photosensitive resin; (2) 5-25 parts of quick-drying type acrylate polymer; (3) 5-15 parts of composition of which the molecules contain more than two olefinic unsaturated groups; (4) 3-10 parts of photoinitiator composition; and (5) 35-50 parts of filler. The invention also relates to a method for preparing the alkaline imaging photosensitive resin composition. The alkaline imaging photosensitive resin composition has the advantages that the formed coating is high in dry-to-touch property (tack-free property), and excellent light sensitivity and resolution can be obtained under low energy, so that the requirements of high-precision circuit etching can be met.
Description
Technical field
The present invention relates to a kind of Photosensitve resin composition, relate in particular to a kind of alkaline video picture type Photosensitve resin composition and preparation method thereof.
Background technology
Traditionally, in the manufacture of printed-wiring board (PWB) (PCB) is produced, use circuit ink to reach the object that circuit forms.So-called circuit ink, refers on covered substrate copper face, utilizes exposure and alkaline video picture to carry out image transfer, and forms the film of special pattern, thereby reach the protective material of anti-etching formation specific circuit.
In recent years, along with miniaturization and, high performance and the high density actual load of electrical equipment, printed circuit board industry is constantly reducing live width and the line-spacing of its circuit, the analytic ability of traditional circuit ink cannot reach the requirement of product, improve exposure energy and can cause suction vacuum error, circuit can not resolved, and reduces exposure energy and can cause again the series of problems such as open circuit breach.Numerous PCB manufacturer is in the product that has high precision to require, and the dry film of use cost costliness replaces traditional circuit ink to reach the requirement of product; But in traditional circuit ink, increase the use amount of sensitization monomer and light trigger, though can improve its analytic ability, its dry to touch (tack-free property) is variation obviously, cannot carry out Industry Promotion.
Summary of the invention
For above-mentioned shortcoming, the object of the present invention is to provide a kind of alkaline video picture type Photosensitve resin composition, the dry to touch (tack-free property) of its film that can form is good and can obtain excellent photonasty and resolution under low-yield, thereby can meet the requirement of high precision circuit etching.
Technology contents of the present invention is: a kind of alkaline video picture type Photosensitve resin composition, is characterized in that it comprises the component of following percentage by weight:
(1), the carboxylic photoresist 20～35 of quick-dry type
(2), quick-dry type acrylate polymer 5～25
(3), in molecule, contain the composition 5～15 of more than 2 compound of olefinic unsaturated group
(4), photoinitiator composite 3～10
(5), filler 35～50
Wherein the acid value of the carboxylic photoresist of quick-dry type is 40～150KOH/g, and solid content is 40～70wt%, and mean molecular weight is 8000～15000, and the carboxylic photoresist of quick-dry type is prepared by following steps:
(A), in organic solvent, add the compound (a) in molecule with more than 2 ring-type ether, then add unsaturated monocarboxylic (b) and catalyzer, at 100～160 DEG C, react 8～36 hours to obtain reaction product (c);
The compound (a) wherein in molecule with more than 2 ring-type ether is Study On O-cresol Epoxy Resin, phenol novolac epoxy resins, bisphenol f type epoxy resin, bisphenol-s epoxy resin or united phenol-type epoxy resin;
Unsaturated monocarboxylic (b) is acrylic or methacrylic acid; The weight ratio in the addition of unsaturated monocarboxylic (b) and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Catalyzer is the trivalent organophosphorus compounds that carbon number is 1～12 alkyl or aryl that has of tertiary phosphine class, is specially triethyl phosphine, tributylphosphine or triphenylphosphine; The use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.2～5.0%;
Organic solvent is the 1-Methoxy-2-propyl acetate of volatility excellence, and its use amount is 0.5～3 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
(B) in the reaction product (c), making, add respectively polymerization inhibitor and after saturated or unsaturated multi-anhydride (d), at 80～150 DEG C, react 6～12 hours to obtain reaction product (e) in step (A);
Saturated or unsaturated multi-anhydride (d) is maleic anhydride, phthalic anhydride, succinic anhydride, THPA or tetrabydrophthalic anhydride; The weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:1～1:3;
Polymerization inhibitor is the substituted phenol compound of phenol, is specially p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
(C) after adding respectively polymerization inhibitor in the reaction product (e), making in step (B) and thering is the compound (f) of olefinic unsaturated group and ring-type ether in molecule, react and within 6～12 hours, be the carboxylic photoresist of finished product quick-dry type at 80～150 DEG C;
The compound (f) in molecule with olefinic unsaturated group and ring-type ether is glycidyl methacrylate or acrylic acid 4-hydroxy butyl ester glycidol ether, and the weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Polymerization inhibitor is the substituted phenol compound of phenol, is specially p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
The acid value of quick-dry type acrylate polymer is 40～150KOH/g, and solid content is 40～70wt%, and mean molecular weight is 5000～10000;
Quick-dry type acrylate polymer is prepared by following method, in organic solvent (I), add unsaturated monocarboxylic (b '), add again the acrylate that contains single olefinic unsaturated group in molecule (a ') and azo-initiator (c '), then at 80～160 DEG C of reactions quick-dry type acrylate polymer that gets product for 8～24 hours;
Wherein in the preparation method of above-mentioned quick-dry type acrylate polymer, and unsaturated monocarboxylic (b ') be acrylic or methacrylic acid;
Organic solvent (I) is 1-Methoxy-2-propyl acetate or the propylene glycol monomethyl ether organic solvent of volatility excellence, and the weight ratio of the addition of organic solvent (I) and unsaturated monocarboxylic (b ') is 2:1～8:1;
The acrylate (a ') that contains single olefinic unsaturated group in molecule is the potpourri in methyl methacrylate and butyl acrylate, methacrylic acid benzyl ester, Isooctyl acrylate monomer or hydroxyethyl methylacrylate; The percentage by weight that methyl methacrylate contains in the acrylate (a ') of single olefinic unsaturated group in molecule is 30～70; In molecule, contain single olefinic unsaturated group acrylate (a ') addition for the weight ratio of unsaturated monocarboxylic (b ') be 2:1～5:1;
Azo-initiator (c ') be oil-soluble azo-initiator, be specially azoisobutyronitrile or ABVN; The addition of azo-initiator (c ') be unsaturated monocarboxylic (b ') weight 1～20%;
In molecule, contain more than 2 olefinic unsaturated group compound composition be the composition of trimethylolpropane triacrylate and dipentaerythritol acrylate, the percentage by weight of trimethylolpropane triacrylate and dipentaerythritol acrylate is 1:1～1:2;
Photoinitiator composite is the component of following percentage by weight:
Tetraethyl michaelis ketone 1～5
Two 2, the luxuriant titanium 0.5～1.5 of the fluoro-3-pyrroles's phenyl two of 6-bis-
2-isopropyl thioxanthone 15～25
2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone 70～80
Filler is the component of following percentage by weight:
Silica 1～5
Porcelain earth 3～10
Talcum powder 85～95;
The mean grain size of silicon dioxide is 4～8um; Kaolinic mean grain size is 4～8um; Talcous mean grain size is 3～8um.
In above-mentioned alkaline video picture type Photosensitve resin composition, the acid value of the carboxylic photoresist of quick-dry type is preferably 50～80 KOH/g.
Preferably 50～80 KOH/g of acid value of quick-dry type acrylate polymer in above-mentioned alkaline video picture type Photosensitve resin composition.
Another object of the present invention is to provide the preparation method of above-mentioned alkaline video picture type Photosensitve resin composition.
A preparation method for alkaline video picture type Photosensitve resin composition, its step is as follows
(1), the preparation of the carboxylic photoresist of quick-dry type, step is as follows:
(A), in organic solvent, add the compound (a) in molecule with more than 2 ring-type ether, then add unsaturated monocarboxylic (b) and catalyzer, at 100～160 DEG C, react 8～36 hours to obtain reaction product (c);
The compound (a) wherein in molecule with more than 2 ring-type ether is Study On O-cresol Epoxy Resin, phenol novolac epoxy resins, bisphenol f type epoxy resin, bisphenol-s epoxy resin or united phenol-type epoxy resin;
Unsaturated monocarboxylic (b) is acrylic or methacrylic acid; The weight ratio in the addition of unsaturated monocarboxylic (b) and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Catalyzer is the trivalent organophosphorus compounds that carbon number is 1～12 alkyl or aryl that has of tertiary phosphine class, is specially triethyl phosphine, tributylphosphine or triphenylphosphine; The use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.2～5.0%;
Organic solvent is the 1-Methoxy-2-propyl acetate of volatility excellence, and its use amount is 0.5～3 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
(B) in the reaction product (c), making, add respectively polymerization inhibitor and after saturated or unsaturated multi-anhydride (d), at 80～150 DEG C, react 6～12 hours to obtain reaction product (e) in step (A);
Saturated or unsaturated multi-anhydride (d) is maleic anhydride, phthalic anhydride, succinic anhydride, THPA or tetrabydrophthalic anhydride; The weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:1～1:3;
Polymerization inhibitor is the substituted phenol compound of phenol, is specially p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
(C) after adding respectively polymerization inhibitor in the reaction product (e), making in step (B) and thering is the compound (f) of olefinic unsaturated group and ring-type ether in molecule, react and within 6～12 hours, be the carboxylic photoresist of finished product quick-dry type at 80～150 DEG C;
The compound (f) wherein in molecule with olefinic unsaturated group and ring-type ether is glycidyl methacrylate or acrylic acid 4-hydroxy butyl ester glycidol ether, and the weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Polymerization inhibitor is the substituted phenol compound of phenol, is specially p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
(2), the preparation of quick-dry type acrylate polymer, in organic solvent (I), add unsaturated monocarboxylic (b '), add again the acrylate that contains single olefinic unsaturated group in molecule (a ') and azo-initiator (c '), then at 80～160 DEG C of reactions quick-dry type acrylate polymer that gets product for 8～24 hours; Wherein
Unsaturated monocarboxylic (b ') be acrylic or methacrylic acid;
Organic solvent (I) is 1-Methoxy-2-propyl acetate or the propylene glycol monomethyl ether organic solvent of volatility excellence, and the weight ratio of the addition of organic solvent (I) and unsaturated monocarboxylic (b ') is 2:1～8:1;
The acrylate (a ') that contains single olefinic unsaturated group in molecule in methyl methacrylate and butyl acrylate, methacrylic acid benzyl ester, Isooctyl acrylate monomer or hydroxyethyl methylacrylate potpourri; The percentage by weight that methyl methacrylate contains in the acrylate (a ') of single olefinic unsaturated group in molecule is 30～70%; In molecule, contain single olefinic unsaturated group acrylate (a ') addition for the weight ratio of unsaturated monocarboxylic (b ') be 2:1～5:1;
Azo-initiator (c ') be oil-soluble azo-initiator, be specially azoisobutyronitrile or ABVN; The addition of azo-initiator (c ') be unsaturated monocarboxylic (b ') weight 1～20%;
(3), the compound, photoinitiator composite and the filler that in the quick-dry type acrylate polymer making in the carboxylic photoresist of quick-dry type making in step (1), step (2), molecule, contain more than 2 olefinic unsaturated group are mixed as following weight percent after both finished product alkalescence video picture type Photosensitve resin composition
The carboxylic photoresist 20～35 of quick-dry type
Quick-dry type acrylate polymer 5～25
In molecule, contain the composition 5～15 of more than 2 compound of olefinic unsaturated group
Photoinitiator composite 3～10
Filler 35～50;
Wherein in molecule, contain more than 2 olefinic unsaturated group compound composition be the composition of trimethylolpropane triacrylate and dipentaerythritol acrylate, the percentage by weight of trimethylolpropane triacrylate and dipentaerythritol acrylate is 1:1～1:2;
Photoinitiator composite is the component of following percentage by weight:
Tetraethyl michaelis ketone 1～5
Two 2, the luxuriant titanium 0.5～1.5 of the fluoro-3-pyrroles's phenyl two of 6-bis-
2-isopropyl thioxanthone 15～25
2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone 70～80
Filler is the component of following percentage by weight:
Silica 1～5
Porcelain earth 3～10
Talcum powder 85～95
The mean grain size of silicon dioxide is 4～8um; Kaolinic mean grain size is 4～8um; Talcous mean grain size is 3～8um.
In the preparation method's of above-mentioned alkaline video picture type Photosensitve resin composition step (1) in the preparation method's of the carboxylic photoresist of quick-dry type step (A), the preferably Study On O-cresol Epoxy Resin of compound (a) in molecule with more than 2 ring-type ether, especially has 70 DEG C of above Study On O-cresol Epoxy Resins of high softening-point; The use amount of catalyzer, be preferably the compound (a) in molecule with more than 2 ring-type ether weight 0.5～3.0%, most preferably be the compound (a) in molecule with more than 2 ring-type ether weight 0.8～2.0%; Preferably 110～130 DEG C of temperature of reaction; Consumption of organic solvent is preferably 0.8～2 times of weight of the compound (a) in molecule with more than 2 ring-type ether, more preferably in molecule, has 1～1.5 times of weight of the compound (a) of more than 2 ring-type ether.
In the preparation method's of above-mentioned alkaline video picture type Photosensitve resin composition step (1) in the preparation method's of the carboxylic photoresist of quick-dry type step (B), the use amount of polymerization inhibitor be preferably the compound (a) in molecule with more than 2 ring-type ether weight 0.1～0.5%, more preferably 0.15～0.3%; Preferably 90～110 DEG C of temperature of reaction.
In the preparation method's of above-mentioned alkaline video picture type Photosensitve resin composition step (1) in the preparation method's of the carboxylic photoresist of quick-dry type step (C), the use amount of polymerization inhibitor be preferably the compound (a) in molecule with more than 2 ring-type ether weight 0.1～0.5%, more preferably 0.15～0.3%; Preferably 90～110 DEG C of temperature of reaction.
The weight ratio of the addition of organic solvent (I) and unsaturated monocarboxylic in the preparation of quick-dry type acrylate polymer in the preparation method's of above-mentioned alkaline video picture type Photosensitve resin composition step (2) (b ') is preferably 3:1～7:1, more preferably 4:1～6:1.
In the preparation method's of above-mentioned alkaline video picture type Photosensitve resin composition step (2), in the preparation of quick-dry type acrylate polymer, temperature of reaction is preferably 85～120 DEG C.
The addition of azo-initiator in the preparation of quick-dry type acrylate polymer in the preparation method's of above-mentioned alkaline video picture type Photosensitve resin composition step (2) (c ') be preferably unsaturated monocarboxylic (b ') weight 3～15%; More preferably 5～10% of the weight of unsaturated monocarboxylic (b ').
The advantage that the present invention has is: it can form film in middle high temperature (80～130 DEG C) prebake conditions after two minutes, dry to touch (tack-free property) excellence, under low-yield, excellent photonasty and resolution can be obtained, thereby the requirement of high precision circuit etching can be met.
Embodiment
Below, though utilize embodiments of the invention etc. can specific description, the present invention is limited by these embodiment not.
In the following example:
Study On O-cresol Epoxy Resin is that manufacture in South Asia, Kunshan, NPCN-703, epoxide number 0.45 equivalent/100g, 81 DEG C of softening points;
Tetraethyl michaelis ketone is that Jiu chemical company produces, JRCure EMK;
Two 2, the luxuriant titanium of the fluoro-3-pyrroles's phenyl two of 6-bis-is that Ciba company produces, IRGACURE 784;
2-isopropyl thioxanthone is that Jiu chemical company produces, JRCure ITX;
2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone is that Jiu chemical company produces, JRCure 907;
Silicon dioxide is that goldschmidt chemical corporation is produced, AEROSIL R974; Mean grain size is 4.5um;
Porcelain earth is that BASF AG produces, Satintone 5; Mean grain size is 5.0um;
Talcum powder is that talcum company of Fuji produces, LMS-200; Mean grain size is 6.0um.
Example 1,
(1), possessing thermometer, reflux condensing tube, in the removable flask of 2L of stirrer, add 360g Study On O-cresol Epoxy Resin, 125g acrylic acid, 2.5g is as the triphenylphosphine of catalyzer, 450g 1-Methoxy-2-propyl acetate is as solvent, then be warmed up to 115 DEG C of reactions 12 hours, after being cooled to again 60 DEG C, add 250g phthalic anhydride, 0.8g is as the p methoxy phenol of polymerization inhibitor, be warmed up to 100 DEG C of reactions 8 hours, after cooling to again 60 DEG C, add glycidyl methacrylate 100g, 0.6g is as the p-dihydroxy-benzene of polymerization inhibitor, control 95 DEG C of reactions of temperature 8 hours, obtain the carboxylic photoresist of a kind of quick-dry type of the present invention, the carboxylic photoresist solid content of this quick-dry type is 65wt%, and acid value is 55～65mgKOH/g, and mean molecular weight is 10000,
(2) in the removable flask of the 2L that possesses thermometer, reflux condensing tube, stirrer, add 90g acrylic acid, 480g 1-Methoxy-2-propyl acetate as solvent, add again potpourri and the 7g ABVN of 200g methyl methacrylate and 100g hydroxyethyl methylacrylate composition, be warmed up to 90 DEG C of reactions 10 hours, obtain the carboxylic photoresist of finished product quick-dry type; The carboxylic photoresist solid content of this quick-dry type is 45wt%, and acid value is 50～60mgKOH/g, and mean molecular weight is 6000;
(3), by the carboxylic photoresist of quick-dry type making in 450 g steps (1), the quick-dry type acrylate polymer making in 400g step (2), 100g trimethylolpropane triacrylate, 100g dipentaerythritol acrylate, 2.5g tetraethyl michaelis ketone, 1g two 2, the luxuriant titanium of the fluoro-3-pyrroles's phenyl two of 6-bis-, 25g2-isopropyl thioxanthone, 90g2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone, 25g silicon dioxide, after mixing, 50g porcelain earth and 800g talcum powder be finished product alkalescence video picture type Photosensitve resin composition.
Example 2, (1), possessing thermometer, reflux condensing tube, in the removable flask of 2L of stirrer, add 360g Study On O-cresol Epoxy Resin, 125g acrylic acid, 2.5g is as the triphenylphosphine of catalyzer, 450g 1-Methoxy-2-propyl acetate is as solvent, then be warmed up to 115 DEG C of reactions 12 hours, after being cooled to again 60 DEG C, add 250g maleic anhydride, 0.8g is as the p methoxy phenol of polymerization inhibitor, be warmed up to 100 DEG C of reactions 8 hours, after cooling to again 60 DEG C, add acrylic acid 4-hydroxy butyl ester glycidol ether 100g, 1.0g is as the p-dihydroxy-benzene of polymerization inhibitor, control 95 DEG C of reactions of temperature 8 hours, obtain the carboxylic photoresist of a kind of quick-dry type of the present invention, the carboxylic photoresist solid content of this quick-dry type is 65wt%, and acid value is 50～60mgKOH/g, and mean molecular weight is 14000,
(2) in the removable flask of the 2L that possesses thermometer, reflux condensing tube, stirrer, add 90g acrylic acid, 480g 1-Methoxy-2-propyl acetate as solvent, add again potpourri and the 7g ABVN of 200g methyl methacrylate and 100g EHMA composition, be warmed up to 90 DEG C of reactions 10 hours, obtain the carboxylic photoresist of finished product quick-dry type; The carboxylic photoresist solid content of this quick-dry type is 45wt%, and acid value is 50～60mgKOH/g, and mean molecular weight is 8000;
(3), by the carboxylic photoresist of quick-dry type making in 610 g steps (1), the quick-dry type acrylate polymer making in 200g step (2), 100g trimethylolpropane triacrylate, 100g dipentaerythritol acrylate, 2.5g tetraethyl michaelis ketone, 1g two 2, the luxuriant titanium of the fluoro-3-pyrroles's phenyl two of 6-bis-, 25g2-isopropyl thioxanthone, 90g2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone, 25g silicon dioxide, after mixing, 50g porcelain earth and 800g talcum powder be finished product alkalescence video picture type Photosensitve resin composition.
The properties of the film that the finished product alkalescence video picture type Photosensitve resin composition of preparation in embodiment 1 and 2 is formed is tested relatively, evaluates, respectively in result shown in table 1.
Table 1
From the result shown in table 1, according to Photosensitve resin composition of the present invention, can obtain dry to touch excellence, can obtain high photosensitivity and excellent resolution in 100 mJ/cm2 energy left and right, and can be by the Photosensitve resin composition of alkaline video picture.
The appraisal procedure of the performance test in above-mentioned table 1 illustrates as follows.
(1) dry to touch
Each test example is coated on copper face substrate, at 120 DEG C of temperature, toasts 2min, by the light film coated surface of pressing of finger, to specific viscosity chirality difference.Determinating reference is as shown in following.
◎: represent dry to touch excellence (not having sticky hand to occur).
Zero: represent dry to touch good (having slight sticky hand to occur).
△: represent dry to touch general (having serious sticky hand to occur).
(2) sensitivity
Use 21 lattice energy gages to cover on the dry coating that each test example forms, utilize respectively 50,100,150, the ultraviolet light of 200mJ/cm2 energy exposes, carry out again alkaline video picture, finally assess lattice after video picture and count the residual lattice number (residual lattice number is the almost lattice number of complete reservation virgin state of film) of table.
Wherein, the mode of alkaline video picture is gunite, and alkaline imaging liquid is the sodium carbonate alkaline aqueous solution of 1.0wt% concentration, and imaging liquid temperature is 30 DEG C, and time of developing is 1min.
(3) resolution
With above-mentioned sensitivity method, use the resolution egative film of 1.5～3.5mil to cover on the dry coating that each test example forms, utilize respectively 50,100,150, the ultraviolet light of 200mJ/cm2 energy exposes, then carries out alkaline video picture, finally assesses complete minimum resolution after video picture.
(4) development point
Each test example is coated on copper face substrate, at 120 DEG C of temperature, toasts 2min, then carry out alkaline video picture, assess the pre-baked rear clean shortest time of painting film development.
Claims (5)
1. an alkaline video picture type Photosensitve resin composition, is characterized in that it comprises the component of following percentage by weight:
(1), the carboxylic photoresist 20～35 of quick-dry type
(2), quick-dry type acrylate polymer 5～25
(3), in molecule, contain the composition 5～15 of more than 2 compound of olefinic unsaturated group
(4), photoinitiator composite 3～10
(5), filler 35～50
Wherein the acid value of the carboxylic photoresist of quick-dry type is 40～150KOH/g, and solid content is 40～70wt%, and mean molecular weight is 8000～15000, and the carboxylic photoresist of quick-dry type is prepared by following steps:
(A), in organic solvent, add the compound (a) in molecule with more than 2 ring-type ether, then add unsaturated monocarboxylic (b) and catalyzer, at 100～160 DEG C, react 8～36 hours to obtain reaction product (c);
The compound (a) wherein in molecule with more than 2 ring-type ether is Study On O-cresol Epoxy Resin, phenol novolac epoxy resins, bisphenol f type epoxy resin, bisphenol-s epoxy resin or united phenol-type epoxy resin;
Unsaturated monocarboxylic (b) is acrylic or methacrylic acid; The weight ratio in the addition of unsaturated monocarboxylic (b) and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Catalyzer is triethyl phosphine, tributylphosphine or triphenylphosphine; The use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.2～5.0%;
Organic solvent is 1-Methoxy-2-propyl acetate, and its use amount is 0.5～3 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
(B) in the reaction product (c), making, add respectively polymerization inhibitor and after saturated or unsaturated multi-anhydride (d), at 80～150 DEG C, react 6～12 hours to obtain reaction product (e) in step (A);
Saturated or unsaturated multi-anhydride (d) is maleic anhydride, phthalic anhydride, succinic anhydride, THPA or tetrabydrophthalic anhydride; The weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:1～1:3;
Polymerization inhibitor is p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
(C) after adding respectively polymerization inhibitor in the reaction product (e), making in step (B) and thering is the compound (f) of olefinic unsaturated group and ring-type ether in molecule, react and within 6～12 hours, be the carboxylic photoresist of finished product quick-dry type at 80～150 DEG C;
The compound (f) in molecule with olefinic unsaturated group and ring-type ether is glycidyl methacrylate or acrylic acid 4-hydroxy butyl ester glycidol ether, and the weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Polymerization inhibitor is p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
The acid value of quick-dry type acrylate polymer is 40～150KOH/g, and solid content is 40～70wt%, and mean molecular weight is 5000～10000;
Quick-dry type acrylate polymer is prepared by following method, in organic solvent (I), add unsaturated monocarboxylic (b '), add again the acrylate that contains single olefinic unsaturated group in molecule (a ') and azo-initiator (c '), then at 80～160 DEG C of reactions quick-dry type acrylate polymer that gets product for 8～24 hours;
In the preparation method of above-mentioned quick-dry type acrylate polymer, and unsaturated monocarboxylic (b ') be acrylic or methacrylic acid;
Organic solvent (I) is 1-Methoxy-2-propyl acetate or propylene glycol monomethyl ether organic solvent, and the weight ratio of the addition of organic solvent (I) and unsaturated monocarboxylic (b ') is 2:1～8:1;
The acrylate (a ') that contains single olefinic unsaturated group in molecule in methyl methacrylate and butyl acrylate, methacrylic acid benzyl ester, Isooctyl acrylate monomer or hydroxyethyl methylacrylate potpourri; The percentage by weight that methyl methacrylate contains in the acrylate (a ') of single olefinic unsaturated group in molecule is 30～70; In molecule, contain single olefinic unsaturated group acrylate (a ') addition for the weight ratio of unsaturated monocarboxylic (b ') be 2:1～5:1;
Azo-initiator (c ') be oil-soluble azo-initiator, be specially azoisobutyronitrile or ABVN; The addition of azo-initiator (c ') be unsaturated monocarboxylic (b ') weight 1～20%;
In molecule, contain more than 2 olefinic unsaturated group compound composition be the composition of trimethylolpropane triacrylate and dipentaerythritol acrylate, the percentage by weight of trimethylolpropane triacrylate and dipentaerythritol acrylate is 1:1～1:2;
Photoinitiator composite is the component of following percentage by weight:
Tetraethyl michaelis ketone 1～5
Two 2, the luxuriant titanium 0.5～1.5 of the fluoro-3-pyrroles's phenyl two of 6-bis-
2-isopropyl thioxanthone 15～25
2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone 70～80
Filler is the component of following percentage by weight:
Silica 1～5
Porcelain earth 3～10
Talcum powder 85～95;
The mean grain size of silicon dioxide is 4～8um; Kaolinic mean grain size is 4～8um; Talcous mean grain size is 3～8um.
2. alkaline video picture type Photosensitve resin composition, is characterized in that the acid value of the carboxylic photoresist of quick-dry type is preferably 50～80 KOH/g; The acid value of quick-dry type acrylate polymer is 50～80 KOH/g preferably.
3. the preparation method of alkaline video picture type Photosensitve resin composition, its step is as follows: the preparation of (1), the carboxylic photoresist of quick-dry type, step is as follows:
(A), in organic solvent, add the compound (a) in molecule with more than 2 ring-type ether, then add unsaturated monocarboxylic (b) and catalyzer, at 100～160 DEG C, react 8～36 hours to obtain reaction product (c);
The compound (a) wherein in molecule with more than 2 ring-type ether is Study On O-cresol Epoxy Resin, phenol novolac epoxy resins, bisphenol f type epoxy resin, bisphenol-s epoxy resin or united phenol-type epoxy resin;
Unsaturated monocarboxylic (b) is acrylic or methacrylic acid; The weight ratio in the addition of unsaturated monocarboxylic (b) and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Catalyzer is triethyl phosphine, tributylphosphine or triphenylphosphine; The use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.2～5.0%;
Organic solvent is 1-Methoxy-2-propyl acetate, and its use amount is 0.5～3 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
(B) in the reaction product (c), making, add respectively polymerization inhibitor and after saturated or unsaturated multi-anhydride (d), at 80～150 DEG C, react 6～12 hours to obtain reaction product (e) in step (A);
Saturated or unsaturated multi-anhydride (d) is maleic anhydride, phthalic anhydride, succinic anhydride, THPA or tetrabydrophthalic anhydride; The weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:1～1:3;
Polymerization inhibitor is p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
(C) after adding respectively polymerization inhibitor in the reaction product (e), making in step (B) and thering is the compound (f) of olefinic unsaturated group and ring-type ether in molecule, react and within 6～12 hours, be the carboxylic photoresist of finished product quick-dry type at 80～150 DEG C;
The compound (f) wherein in molecule with olefinic unsaturated group and ring-type ether is glycidyl methacrylate or acrylic acid 4-hydroxy butyl ester glycidol ether, and the weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Polymerization inhibitor is p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
(2), the preparation of quick-dry type acrylate polymer, in organic solvent (I), add unsaturated monocarboxylic (b '), add again the acrylate that contains single olefinic unsaturated group in molecule (a ') and azo-initiator (c '), then at 80～160 DEG C of reactions quick-dry type acrylate polymer that gets product for 8～24 hours; Wherein
Unsaturated monocarboxylic (b ') be acrylic or methacrylic acid;
Organic solvent (I) is 1-Methoxy-2-propyl acetate or propylene glycol monomethyl ether organic solvent, and the weight ratio of the addition of organic solvent (I) and unsaturated monocarboxylic (b ') is 2:1～8:1;
The acrylate (a ') that contains single olefinic unsaturated group in molecule is the potpourri in methyl methacrylate and butyl acrylate, methacrylic acid benzyl ester, Isooctyl acrylate monomer or hydroxyethyl methylacrylate; The percentage by weight that methyl methacrylate contains in the acrylate (a ') of single olefinic unsaturated group in molecule is 30～70%; In molecule, contain single olefinic unsaturated group acrylate (a ') addition for the weight ratio of unsaturated monocarboxylic (b ') be 2:1～5:1;
Azo-initiator (c ') be oil-soluble azo-initiator, be specially azoisobutyronitrile or ABVN; The addition of azo-initiator (c ') be unsaturated monocarboxylic (b ') weight 1～20%;
(3), the compound, photoinitiator composite and the filler that in the quick-dry type acrylate polymer making in the carboxylic photoresist of quick-dry type making in step (1), step (2), molecule, contain more than 2 olefinic unsaturated group are mixed as following weight percent after both finished product alkalescence video picture type Photosensitve resin composition
The carboxylic photoresist 20～35 of quick-dry type
Quick-dry type acrylate polymer 5～25
In molecule, contain the composition 5～15 of more than 2 compound of olefinic unsaturated group
Photoinitiator composite 3～10
Filler 35～50;
Wherein in molecule, contain more than 2 olefinic unsaturated group compound composition be the composition of trimethylolpropane triacrylate and dipentaerythritol acrylate, the percentage by weight of trimethylolpropane triacrylate and dipentaerythritol acrylate is 1:1～1:2;
Photoinitiator composite is the component of following percentage by weight:
Tetraethyl michaelis ketone 1～5
Two 2, the luxuriant titanium 0.5～1.5 of the fluoro-3-pyrroles's phenyl two of 6-bis-
2-isopropyl thioxanthone 15～25
2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone 70～80
Filler is the component of following percentage by weight:
Silica 1～5
Porcelain earth 3～10
Talcum powder 85～95
The mean grain size of silicon dioxide is 4～8um; Kaolinic mean grain size is 4～8um; Talcous mean grain size is 3～8um.
4. the preparation method of alkaline video picture type Photosensitve resin composition according to claim 3, it is characterized in that, in the preparation method's of the carboxylic photoresist of quick-dry type step (A), the compound (a) in molecule with more than 2 ring-type ether is Study On O-cresol Epoxy Resin; The use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.5～3.0%; Temperature of reaction is 110～130 DEG C; Consumption of organic solvent is 0.8～2 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
In the preparation method's of the carboxylic photoresist of quick-dry type step (B), the use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.1～0.5%; Temperature of reaction is 90～110 DEG C;
In the preparation method's of the carboxylic photoresist of quick-dry type step (C), the use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.1～0.5%; Temperature of reaction is 90～110 DEG C;
The weight ratio of the addition of organic solvent in the preparation of quick-dry type acrylate polymer (I) and unsaturated monocarboxylic (b ') is 3:1～7:1;
In the preparation of quick-dry type acrylate polymer, temperature of reaction is 85～120 DEG C;
The addition of azo-initiator in the preparation of quick-dry type acrylate polymer (c ') be unsaturated monocarboxylic (b ') weight 3～15%.
5. the preparation method of alkaline video picture type Photosensitve resin composition, it is characterized in that in the preparation method's of the carboxylic photoresist of quick-dry type step (A), the use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.8～2.0%; Consumption of organic solvent is 1～1.5 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
In the preparation method's of the carboxylic photoresist of quick-dry type step (B), the use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.15～0.3%;
In the preparation method's of the carboxylic photoresist of quick-dry type step (C), the use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.15～0.3%;
The weight ratio of the addition of organic solvent in the preparation of quick-dry type acrylate polymer (I) and unsaturated monocarboxylic (b ') is 4:1～6:1;
The addition of azo-initiator in the preparation of quick-dry type acrylate polymer (c ') is 5～10% of unsaturated monocarboxylic (b ').
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| CN115109456A (en) * | 2022-06-24 | 2022-09-27 | 广州市红太电子科技有限公司 | Photosensitive developing type solder resist ink for flexible circuit board |
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