JPH0868000A - Electrodepositable double layer resist - Google Patents

Abstract

PURPOSE: To obtain a photosensitive electrodeposition-coated article substantially free from developing and etching residues by applying a non-photosensitive layer on an electrically conductive article, then immersing this article into an electrodeposition coating compsn. capable of forming a photoimage and supplying current thereto.

CONSTITUTION: The non-photosensitive layer contg. a water dispersible acid or alkaline soluble resin having an acid value of 20 to 300 is applied on the electrically conductive substrate. The substrate is then immersed into the electrodeposition coating compsn. capable of forming a photoimage and current is supplied to the article as an anode, to form the electrodeposited layer on the surface of the non-photosensitive layer. The electrically conductive article is an article which can be functioned as the anode by a deposition method of anodic electrophoresis. The non-photosensitive layer is formed to have a thickness of about 1 to 10 microns. The electrodeposition-coated layer is obtd. by electrodeposition coating from the electrodeposition coating compsn. of a positive charge consisting of the water soluble or water dispersible resin having the acid value of 20 to 300 and a number average mol.wt. of at least 2,000 and an initiator.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to bilayer coatings on electrically conductive articles, one layer of which is an electrodeposited resist.
More specifically, the present invention relates to a bilayer coating on a printed wiring board, one layer of which is photoresist.

[0002]

BACKGROUND OF THE INVENTION The present invention relates to liquid photoresists and methods of electrophoresis for depositing such films on conductive surfaces. Electrophoresis refers to the movement of charged particles or molecules through a liquid medium under the influence of an applied electric field. Electrophoretic deposition or electrodeposition is carried out in an electrolytic cell in which the surface of a conductive material coated with moving charged particles acts as an electrode. Electrodeposition of cationic polymers on the surface of a negatively charged electrode (cathode) (positively charged polymer) is called cathodic electrophoresis, while on the surface of a positively charged electrode (anode). The electrophoretic deposition of anionic polymers (negatively charged polymers) is called anodic electrophoresis.

The subject of electrophoretic coating materials is well known and is widely used for coating metal surfaces such as automobiles. Electrophoresis has been used for electronic components such as resistors and capacitors, which are essential for printed wiring boards. It is also known to use electrophoresis to deposit non-photoactive thermosetting coatings. Electrodeposition of photosensitive coatings by anodic electrophoresis is described in US Pat. No. 3,738,835. Electrodeposition of photosensitive coatings by cathodic electrophoresis is described in US Pat.
92,816.

Electrodeposition of a photosensitive coating on a conductive substrate, for example by anodic electrophoresis followed by exposure and development, results in the development and etching residues left on the conductive substrate. For example, when the conductive substrate is copper, it is believed that the copper ions generated by anodic electrophoresis complex with the photosensitive coating and that exposure and development of the photosensitive coating produce these residues.
Other mechanisms, such as metal catalyzed crosslinking or resist degradation, may include development formation and etching residues on the surface of the metal.

Metal chelating agents are described in US Pat.
In at least some cases, such as in 1,854 and 4,845,012, it has been found to be effective in developing clean electrodeposited photoresist. However, there are some cases where chelating agents are not effective, ie, they interfere with the functional groups of the resist.

There is a need for an electrodeposited coating composition that minimizes development and etching residues without the need to reformulate the photoimageable electrodeposition coating composition. Surprisingly and unexpectedly, the addition of a non-photosensitive layer between the electrically conductive article and the photoimageable electrodeposition coated layer provides substantially no development and etch residue, A light-sensitive electrodeposition-coated article is obtained.

[0007]

SUMMARY OF THE INVENTION One aspect of the present invention is: (a) an electrically conductive article; (b) a water-dispersible, acid- or alkali-soluble resin-containing non-photosensitive resin having an acid value of 20 to 300. And (c) a photoimageable electrodeposited layer; providing a photosensitive electrodeposited article substantially free of development and etch residues.

Another aspect of the present invention is: (a) applying a water-dispersible, non-photosensitive layer containing an acid- or alkali-soluble resin having an acid value of 20 to 300 onto an electrically conductive article. (B) dipping an electrically conductive article having a non-photosensitive layer thereon in a photoimageable electrodeposition coating composition; and (c) non-photosensitive by supplying electrical current to the article as an anode. Forming an electrodeposition coated layer on the surface of the electrically conductive layer; and providing a method for electrodeposition of a coating film on an electrically conductive article.

The photoimageable electrodeposition coated layer is (1)
A water-soluble or water-dispersible resin having an acid number of 20 to 300 and a number average molecular weight of at least 2000; and
(2) A positive electrodeposition coating composition comprising an initiator or an initiator system can be used for electrodeposition coating.

In another embodiment, the positive electrodeposition coating composition comprises (a) (1) an acid labile side chain group (pendant acid labile).
groups) and (2) a polymeric material having free acid groups, the polymeric material having an acid number of 25 to 300 and a number average molecular weight of at least 2000; and (b) exposure to actinic radiation to form an acid. A substance that does.

The photoimageable electrodeposition coated layer is (1)
Water-soluble or water-dispersible polymerizable resin having an acid value of 20 to 300 and a number average molecular weight of not less than 300, but 150 to 3000 when the resin is unsaturated.
A negative electrodeposition coating composition comprising: (2) an initiator or initiating system; It can be electrodeposited. The present invention is particularly well suited for use in photoresist coatings on printed wiring boards.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises, in order: (a) an electrically conductive article; (b) a non-photosensitive layer containing a water-dispersible acid or alkali-soluble resin having an acid value of 20 to 300; and (c) a photoimageable electrodeposition-coated layer as defined above; and substantially free of development and etch residue, a photoimageable electrodeposition-coated article.
The present invention also provides a non-photosensitive layer by immersing an electrically conductive article having a non-photosensitive layer thereon in a photoimageable electrodeposition coating composition, followed by applying current to the article as an anode. A method for electrodeposition of a coating film on an electrically conductive article comprising the step of forming an electrodeposition coating composition on the surface of the. Wherein the photoimageable electrodeposition coating composition is an electrodeposition resist coating composition and the electrodeposition coated layer is a photoresist coating on a printed wiring board having a non-photosensitive layer thereon, The preferred embodiments will be described in detail with particular reference.

[Electrically Conductive Article] The electrically conductive article is an electrically conductive substrate that can function as an anode by an anodic deposition method. The conductive article can be selected from copper or other metal clad, three-dimensional objects or thin metal sheets used in photochemical milling processes, such as a copper clad epoxy glass substrate.

[Non-Photosensitive Layer] The non-photosensitive layer contains 20 to 3
Water-dispersible, acid- or alkali-soluble resins or saturated polymers having an acid number of 00 are included. The non-photosensitive layer has a thickness of 1-10 microns, preferably 2-5 microns. If the thickness of the non-photosensitive layer is greater than 20 microns, electrodeposition of the electrodeposited resist coating composition may be hindered. The non-photosensitive layer can be applied by any method known to those skilled in the art, such as dip coating, lamination, electrodeposition and the like. The water dispersible, acid or alkali soluble resins or saturated polymers used in the non-photosensitive layers of the present invention are typically addition or condensation polymers having carrier groups. Addition polymers having carrier groups made from monomers having ethylenic unsaturation are preferred. A carrier group is defined as a group attached to a polymer that can be positively or negatively charged. Polymers containing carrier groups useful in the non-photosensitive layer include acrylic polymers, vinyl polymers other than acrylic polymers, epoxy polymers, polyurethanes,
Includes polyesters and polyamides. Negatively charged carrier groups or anodic electrophoresis (anaphoreti
Carrier groups in c) include groups that react negatively with bases, such as carboxylic acid groups. Ammonia is a base that is useful for ionizing these carrier groups,
Triethylamine, hydroxyethylamine and the like are included.

Positively charged carrier groups or cathophoretic cataphoretic carrier groups include groups that become positively charged upon reaction with an acid, such as amines. Acids useful for protonating the carrier group include:
Includes lactic acid, hydrochloric acid, acetic acid and phosphoric acid.

Acrylic polymers containing carrier groups are prepared by polymerizing or copolymerizing acrylic acid, methacrylic acid, their esters or amides and mixtures of such monomers, provided that at least one monomer contains a carrier group. To be done. In an acrylic polymer having a carrier group for cathodic electrophoresis, one of the monomers has a basic amine group, such as 2- (dimethylamino) ethylmethacrylate (DMAEMA) or 3- (dimethylamino) propylmethacrylamide (DMAPMA).
Can be prepared by polymerizing monomers. For example, reaction with an acid such as lactic acid converts amine groups on the polymer into positively charged amine salts. Similarly, a (meth) acrylic acid polymer having a carrier group for anodic electrophoresis has 1 to about 8 alkyl groups.
A lower alkyl acrylic or methacrylic acid ester containing 4 carbon atoms, such as acrylic or methacrylic acid monomers such as methyl methacrylate, butyl acrylate, etc., alone or with other monomers. The side chain carboxylic acid on the poly (meth) acrylic acid polymer is
It is then converted to a negatively charged carboxylate salt by reacting with a base such as triethylamine.

Alternatively, it is possible to modify the polymer without carrier groups to incorporate such carrier groups. For example, a glycidyl methacrylate polymer can be reacted with an amine to attach an amine carrier group to the polymer chain.

Other than the acrylic or methacrylic polymers mentioned above, vinyl polymers incorporating carrier groups can also be used. These polymers include vinyl monomers such as styrene and substituted styrenes, vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate and vinyl ethers such as methyl vinyl ether, other vinyl monomers alone or with a carrier group such as 2-methyl vinyl. It can be prepared by the polymerization of vinylimidazole containing imidazole and cathodic electrophoretic carrier groups.

Polymers suitable for the practice of this invention can also be prepared by polymerization of acrylic or methacrylic monomers with other vinyl monomers, provided that at least one of the monomers contains a carrier group.

A preferred class of polymers suitable for anodic electrophoresis is by free radical polymerization in a suitable solvent of esters and / or amides of acrylic acid and / or methacrylic acid in which at least one of the monomers contains a carboxylic acid carrier group. It can be manufactured. Suitable solvents for the polymerization include monopropyl ether of 1,2-propanediol (eg Propasol ^(T) -P manufactured by Union Carbide Corporation), methyl cellosolve,
Ethyl cellosorob, butyl cellosorob, cellosolve acetate, methyl carbitol, butyl carbitol,
1,2-dimethoxyethane, diethylene glycol dimethyl ether, isopropanol, propanol, n-
Butanol, secondary butanol, isobutanol, cyclohexanol, ethylene glycol, 1,3-propanediol, acetone, meethylethylketone, methylisobutyl, tetrahydrofuran, ethyl acetate, butyl acetate, 1,4-dioxane, toluene, xylene, Includes acetonitrile, dimethylformamide and dimethylsulfoxide.

The polymer or polymer mixture containing carrier groups is typically a polymer or polymer mixture 1.
At least about 10 milliequivalents of charged carrier groups per 100 g (polymer or polymer mixture in water dispersible,
At least about 200 milliequivalents of charged carrier groups per 100 g of polymer or polymer mixture (to enable it to be electrophoretically deposited as a film) to adversely affect the exposed areas of the layer by the non-photosensitive layer deposited by electrophoresis. In order to enable selective development, no) is contained. The milliequivalent of charged carrier groups per 100 g of polymer (meq / 100 g) is the carrier group for anodic electrophoresis, where each equivalent of added base is the ionization of a carboxylic acid on the respective group, eg, polymer. It is calculated based on the assumption.

For anodic electrophoretic polymers containing negatively charged carrier groups, the polymer is about 20-100.
It is preferable to include meq / 100 g. The molecular weight of the polymers used in the non-photosensitive layer of the present invention is typically 100,
It should not be greater than 000 weight average molecular weight. If acrylic, methacrylic or other vinyl polymers containing carrier groups are used, the number average molecular weight is about 10,
000 to about 100,000, and preferably about 20,000
It should be in the range of number average molecular weight from 0 to about 60,000.

Photoimageable Electrodeposited Layer The photoimageable electrodeposition coated layer is electrodeposited on the non-photosensitive layer present on the electrically conductive article. It is coated from a photoimageable electrodeposition coating composition which can be positive or negative. The positive electrodeposition coating composition comprises (1) a water soluble or water dispersible resin having an acid number of 20 to 300 and a number average molecular weight of at least 2000; and (2) an initiator or initiation system.

Further, the positive electrodeposition coating composition is (a) a polymer substance having (1) an acid labile side chain group and (2) a free acid group.
It has an acid number of 300 and a number average molecular weight of at least 2000; and (b) a substance that is exposed to actinic radiation to form an acid.

The negative electrodeposition coating composition is (1) 20-30
A water-soluble or water-dispersible polymerizable resin having an acid number of 0 and a number average molecular weight not less than 300, provided that the resin has an unsaturated equivalent weight of 150 to 3000, and the resin is Used in combination with ethylenically unsaturated compounds when saturated; and (2)
Initiator or initiator system; The ethylenically unsaturated compound is typically a (meth) acrylic monomer that can typically be used in combination with the unsaturated resin in the composition. Dyes can optionally be present in the electrodeposition coating composition.

[Positive Electrodeposition Coating Composition] The resin used in the case of the positive resist of the present invention may have the same properties as the above resin for use in the non-photosensitive layer. In addition, it can have a positive resist initiator covalently attached to it. Initiators for positive electrodeposition coating compositions include
Included are the reaction products of diazoquinone derivatives such as 2-diazo-1-naphthol-5-sulfonyl chloride with trihydrobenzophenone, or other hydroxy containing aromatic compounds well known to those skilled in the art. The initiator is covalently attached to the polymer. Other water insoluble acid precursors such as aromatic onium salts can also be used. These initiators typically act as solubility inhibitors before exposure and as solubility promoters after exposure.

Another positive electrodeposition coating composition may consist of a polymeric material having acid labile side groups and free acid groups and a material that produces an acid upon exposure to actinic radiation. These compositions are disclosed in US Pat. No. 5,252,427, issued Oct. 12, 1993, the disclosure of which is incorporated herein by reference.

[Negative Electrodeposition Coating Composition] Water-soluble or water-dispersible polymerizable unsaturated resin: The polymerizable unsaturated resin (a) used in the present invention has at least a polymer main chain or a side chain. It is a resin containing one radically polymerizable unsaturated bond. The polymerizable unsaturated resin (a) can be selected from the following resins (1) to (5). (1) A polymerizable unsaturated resin obtained by adding an equimolar addition product of a hydroxyl group-containing unsaturated compound and a diisocyanate compound to a hydroxyl group-containing acrylic resin having a high acid value; (2) α, β- A mixture of a polymerizable unsaturated resin and an ethylenically unsaturated compound obtained by adding an ethylenically unsaturated dibasic acid or an anhydride thereof to an unsaturated bond of a fatty acid chain in an ester of an epoxy resin and an unsaturated fatty acid. An epoxy resin is a compound having a relatively high molecular weight and containing at least one epoxy resin in one molecule; (3) A mixture of an unsaturated fatty acid-modified alkyd resin having a high acid value and an ethylenically unsaturated compound. (4) Polymerizable unsaturated resin composed of maleated oil and a mixture of ethylenically unsaturated compounds; and (5) Polymerizable obtained by adding a glycidyl group-containing unsaturated compound to an acrylic resin having a high acid value. Unsaturated resin.

The polymerizable unsaturated resin (a) is described in further detail in US Pat. No. 4,845,012 issued Jan. 4, 1989. These copolymerizable,
As the unsaturated resin, the resin (5) is preferable because it is excellent in both photosensitivity and electrodeposition and produces a clean finish. The above-mentioned polymerizable unsaturated resin preferably has a glass transition temperature (Tg) of 0 to 100 ° C, preferably 20 to 70 ° C in addition to the acid value, unsaturated equivalent weight and number average molecular weight. When the Tg of the polymerizable unsaturated resin is below 0 ° C., the electrodeposition coated layer is tacky and dust or other impurities tend to adhere to the coated layer, or the coated layer is Difficult to handle. Tg is 100 ° C
If it exceeds, the electrodeposited layer becomes hard and may form cracks.

The polymerizable unsaturated resin of the present invention is water-dispersible or water-soluble, and the water-dispersed or water-solubilized resin is an acid group contained in the skeleton of the polymerizable unsaturated resin, such as a carboxylic acid group. Is neutralized with an alkali (neutralizing agent). Examples of neutralizing agents are alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine and diisobutylamine; alkylalkanolamines such as dimethylaminoethanol. Alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and ammonia. These can be used alone or as a mixture of two or more. The amount of the neutralizing agent is 0.3 to per mol of acid groups contained in the resin skeleton.
1.0 equivalent is preferred. If the quantity is less than 0.3 equivalent,
The water dispersibility is reduced, which makes electrodeposition difficult. If the amount is more than 1.0 equivalent, the storage stability tends to decrease.

Ethylenically unsaturated compounds: The unsaturated or saturated resins mentioned above are ethylenically unsaturated compounds, preferably monounsaturated or polyunsaturated (meth) acrylic monomers, such as alkyl (meth) acrylates (C1-C1). C1
8) Esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and octyl (meth) acrylate; vinyl aromatic compounds such as styrene, vinyltoluene and vinylbenzene; and oligomers such as diethylene glycol di ( Included are (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (-meth) acrylate and pentaerythritol tri (meth) acrylate.

Although the amount of the ethylenically unsaturated compound used as an optional component together with the polymerizable unsaturated resins (1) to (5) or as an essential component together with the saturated resin is not strictly limited, It can vary in its type or type of polymerizable unsaturated or saturated resin. This is usually not more than 100 parts by weight, preferably 1 to 50 parts by weight, per 10 parts by weight of polymerizable unsaturated or saturated resin.

Initiator: The photopolymerization initiator used in the composition of the present invention may be any photopolymerization initiator commonly used in photocurable resin compositions of this type. It is preferably water insoluble. Some suitable photoinitiators are disclosed in U.S. Pat. No. 4,845,012 issued Jul. 4, 1989. The amount of photoinitiator will vary depending on its type or desired cure rate. This is a polymerizable unsaturated or saturated resin component 10
0.1 to 15 parts by weight per 0 parts by weight, preferably 2-1
It can be used in an amount of 0 parts by weight, and more preferably 2 to 8 parts by weight.

[Additive] The photoimageable electrodeposition coating composition of the present invention comprises a conventional resin binder, for example, the polymerizable unsaturated resin or a polymerizable unsaturated group-containing resin different from the saturated resin. Can be included. Examples of the polymerizable unsaturated group-containing resin include those obtained by introducing an ethylenically unsaturated group into the resin, such as polyester acrylate resin, polyurethane resin, epoxy resin and acrylic resin. Examples of the saturated resin include polyester resin, polyurethane resin, epoxy resin and acrylic resin. If additional resin binders are used, no more than 100 parts by weight, preferably 1-50, per 100 parts by weight of polymerizable unsaturated or saturated resin is provided, so that the properties of the coated layer are appropriately adjusted. It can be blended in an amount of parts by weight.

The non-photosensitive and / or photoimageable electrodeposition coating composition of the present invention comprises a surfactant such as polyoxyethylene alkylphenol, polyoxyethylene,
Included are polyoxypropylene, polyoxybutylene, or combinations thereof; anionic or cationic surfactants, fluorinated surfactants and the like.

The water-solubilized or water-dispersible polymerizable unsaturated or saturated resin by neutralization may optionally include a hydrophilic solvent to improve the flowability of the resin components. Examples of hydrophilic solvents include alcohols such as isopropanol, n-butanol, t-butanol, methoxyethanol, ethoxyethanol, butoxyethanol and diethylene glycol; and ethers such as methyl ether, dioxane and tetrahydrofuran. When a hydrophilic solvent is used, its amount is generally 30 per 100 parts by weight of the resin component.
It does not exceed 0 part by weight, preferably 1 to 100 parts by weight.

It is also possible to optionally add a hydrophobic solvent to the water-solubilized or water-dispersible polymerizable unsaturated or saturated resin in order to increase the amount of coating on the material to be coated. it can. Examples of hydrophobic solvents include petroleum solvents such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; higher alcohols such as 2-ethylhexyl alcohol and cyclohexanol. The amount of the hydrophobic solvent generally does not exceed 200 parts by weight, preferably 1 to 100 parts by weight, per 100 parts by weight of the resin component.

The electrodeposition resist coating composition may contain a metal salt of a β-diketone to improve alkaline etch resistance without destabilizing the emulsion or adversely affecting the quality of the coating. it can.

The electrodeposition resist coating composition may also contain pigments known to those skilled in the art. Some preferred dyes include Sudan ^(T) Blue 670 and Sudan ^(T)
Includes red.

[Method] The electrodeposition coating layer is applied to the printed circuit board having a non-photosensitive layer thereon by using the photoimageable electrodeposition coating composition in the following method. For example, an electrodeposition coating bath containing a polymerizable unsaturated or saturated resin, a photopolymerization initiator and optionally an ethylenically unsaturated compound, which are water-solubilized or water-dispersed by neutralization as described above as a main component. Is controlled to a pH of 6.5-9. The bath concentration is maintained at 3 to 25% by weight, based on non-volatile components, and at 15 to 40 ° C, preferably 15 to 30 ° C. A copper clad epoxy glass substrate having a non-photosensitive layer thereon and acting as an anode is dipped in a photocurable electrodeposition coating composition and 40-400.
A DC current of V was passed. The length of time that the electric current passes is 15 seconds to 5 minutes and when dried results in a film having a thickness of 5 to 100 μ, preferably 20 to 60 μ.

A method of electrodeposition of positive electrodeposition coating compositions containing polymeric materials having acid labile side groups and free acid groups and materials which form an acid upon exposure to actinic radiation is described in October 1993. It is disclosed in U.S. Pat. No. 5,252,427 issued 12th. The electrodeposited coating is withdrawn from the electrodeposition coating bath and washed with water. The coating is then dried using conventional heating means such as hot air.

In another embodiment, both the non-photosensitive and photoimageable layers are electrodeposited. The uncured electrodeposited layer is then imaged with the underlying non-photosensitive layer through the target and unexposed areas of the negative resist and exposed areas of the positive resist, which areas are known to those skilled in the art. Washed off using known techniques. The substrate is then etched using conventional techniques to obtain a printed circuit on the substrate.

In the examples below, parts and percentages are by weight unless otherwise stated and are intended to be illustrative and not limiting of the invention.

[0044]

EXAMPLE A polymer, diazoquinone and emulsion were prepared as follows.
Produced using the method. Method 1-Preparation of Polymer A Mechanical stirrer, reflux condenser, nitrogen inlet and addition
In a three-necked round-bottomed flask equipped with a heating funnel,
Acrylate 118g, methyl methacrylate 46
g, hydroxyethyl methacrylate 13.4 g, mac
Roman solution^a)115.8 g and methyl ethyl ketone
(MEK) 70g was added. Bring this to 65 ° C under nitrogen
Heat and, at this time, VASO in 5g of MEK^(T)Open 67
0.735 g of initiator was added through the addition funnel. About 3
After heating for 0 minutes or more, the flask begins to reflux at 90 ° C.
It was Stir the reaction mixture over the next hour to increase.
It started to stick and more than 60 g of MEK was added. The temperature is
Peaks at 93 ° C, then falls slightly and 8
Maintained between 0 and 85 ° C. 2 hours later, in MEK 2g
VASO^(T)Another 0.1225 g aliquot of 67, continued
VASO in MEK 2g ^(T)Consisting of 0.061g of
Another was added in 6 hours. After 9 hours, the temperature drops to room temperature
I got angry. 372 g of polymer solution (measured as 58% solids
Were placed in a round bottom flask, and butyl cellosolve 2
15 g was added. Then MEK is rotary evaporated
It was removed on a filter to obtain 430 g of 50% polymer solution.
It was The measured acid number of this polymer was 48 and
The weight average molecular weight was 58,490.^a)Macroma
-The solution is butylmethac in the ratio 43: 2: 30: 25
Relate / Methyl methacrylate / Hydroxyethyl ester
One end containing the monomer of tacrylate / methacrylic acid
2000 MW oligomer with acrylic unsaturation in
is there.

Method 2-Preparation of diazoquinone A Novolac ^(T) resin SD792A (100% p-tert-butylphenol novolac resin, weight average molecular weight 597,
Borden Packaging and Industrial Products, Louisvil
25 g (obtained from Le, Kentucky) was dissolved in 250 ml of methylene chloride in a 500 ml round bottom flask. To this was added 41.65 g of 2-diazo-1-naphthoyl-5-sulfonyl chloride, with stirring until dissolved, followed by the addition of 15.8 g of triethylamine. The reaction was stirred under dry nitrogen overnight. The reaction mixture is deionized water 100m
It was washed 3 times with I, once with 5% aqueous hydrochloric acid and once with deionized water. The organic phase was dried over anhydrous sodium sulphate and the methylene chloride was removed on a rotary evaporator under reduced pressure, keeping the temperature of the water bath below 35-40 ° C. This method yielded 57 grams of powdered orange flakes.

Method 3-Preparation of Emulsion In a standard 1000 ml 3-neck flask with a thermometer inlet, 500 ml venting dropping funnel and Master Ser for measuring rotation / min (RPM) and stir bar torque.
A stir bar attached to the vodyne Unit was attached. The shape and size of the stirring blade of Teflon ^(T) is important.
It has the shape of an ellipse, but its edges are sharp. The tip-to-tip size was 6 cm and the width was 2 cm. Third
The inlet was used to add to the flask all components except the triethylamine needed to neutralize the polymer. A partition was placed at the thermometer inlet. Triethylamine is very volatile and is used in very small amounts so it was injected into the flask through a septum from a weighed 2 cc glass syringe.

68 g of a solution of polymer A, optionally 6 g of diazoquinone A, 4 g of benzyl alcohol and 16 g of dimethyl diglyme were weighed into a flask. The mixture was stirred until everything dissolved. The flask was then cooled with ice and 0.435 g of triethylamine was poured into the solution over a period of a few minutes while mixing for at least 15 minutes. Then stirrer RPM 1000R
The PM was increased and 405 g of distilled water was added dropwise at a rate of 2 ml / min. The total amount of water added, RPM, torque and time were recorded. At this point in the invention from water-in-oil to oil-in-water emulsions, the stirrer RPM is reduced so that the liquid does not splash because the viscosity drops dramatically. Water was then added at a faster rate. When producing Photoactive Resist Emulsion 1, diazoquinone A was added. It was omitted when polymer emulsion 1 was prepared. The emulsion was electrodeposited using the following method.

Method 4-Electrodeposition A 10 × 20 cm 1 ounce copper-clad epoxy / fiberglass panel was prepared for electropainting by washing with a 320 grit brush in a Chemcut scrubber. The emulsion was electrodeposited at 50 mA / dm ² using a Hawlett Packard 6035A DC power supply in a polyethylene cell about 10 cm wide, 5 cm deep and 20 cm high with a stainless steel cathode. After painting, the panels were rinsed with distilled water for 20-30 seconds and blown dry with air. To obtain a second coating layer, dip the coated panel in a second emulsion and use the same power source at 50 mA /
The coating was electrodeposited at dm ² . The panels were then rinsed, blown air again to dry and allowed to coalesce at 90 ° C for 10 minutes. Expose and develop the panel using the following method,
And tested.

Method 5-Exposure and Development Coated resist coated panels using Mimir ^(T) 922
A exposed on a 4UV exposure device and equipped with conveyor equipment
0.75% Na _{2 on} SI 757 spray processor
Developed in CO ₃ .H ₂ O at 32-35 ° C. Exposure energy is International with XRL1140B detector
It was monitored using a light model 1400A radiometer.

Method 6-Residual Coating Testing For testing of etch-retarded coating residues, during the 115% of the time required to etch off all the copper on the panels not coated with resist, Panels were sprayed with 55 ° C acidic cupric chloride etchant in an etch machine with a Master conveyor facility. Panels with most of the surface still copper covered after etching are believed to have etch retarding coating residues.

Method 7-Resist Thickness The resist thickness was measured by the difference in weight. Typical
Is a strip from the resist coated panel in question.
Cut, dry at 90 ° C for 10 minutes, cool to room temperature, and
And weighed 10.1 mg. Next, the resist is heated to 55 ° C,
It was removed by maceration in 3% NaOH. Panel with distilled water
Rinse, dry at 90 ° C for 10 minutes, cool to room temperature, and
And reweighed. Resist thickness is 1 resist density
g / cm ³Assuming that the difference in weight and the painting area
Calculated.

Example 1 A polymer emulsion was electrodeposited according to Method 4 above for 27 seconds. The thickness measured by Method 7 was 5.1 microns. (At this thickness, the coating can be washed off in approximately 35 seconds. The panels coated with polymer from Polymer Emulsion 1 were then electrodeposited with Photoactive Resist Emulsion 1 for 12 seconds according to Method 4. Method 7 The average thickness of both coatings, as measured by, was 7-9 microns on average and 2-4 microns for the photoactive resist coating.

The panel was placed at 500 mj / cm according to Method 5.
Exposed at ² . The exposed and unexposed panels were developed according to Method 5 for a continuous time of 0 to 100 seconds, and the resist thickness was measured according to Method 7.
The exposed panel loses more weight (less resist remaining) than the unexposed panel at a given development time.

The developed panel was etched according to Method 6 to check for residue. Both the exposed and unexposed panels were cleanly etched after sufficient development time, while the exposed panels were run with shorter development times. This shows the contrast required for positive photoresist. The thickness and remaining copper data are summarized in Table 1.

[0055]

[Table 1] Weight loss vs. development time 2 layers Coating exposure (mj / cm ² ) Development time (sec) Residual resist (micron) Residual copper 0 0 9.3 Yes 0 58 8.2 Yes 0 67 4.9 Yes 0 100 1.4 No 500 20 8.9 Yes 500 39 9.1 Yes 500 39 6.0 Yes 500 58 58 1.9 Only 500 77 77 1.3 No

Comparative Example Photoactive Resist Emulsion 1 according to Method 4 for 50 seconds for 50 seconds.
It was electrodeposited on the panel at mA / dm ² . The coating thickness averaged 2.8 to 4.1 microns. Five panels were exposed according to Method 5 at 500 mj / cm ² and developed for 58-400 seconds. 1 more according to method 5
Each panel was exposed at 1000 mj / cm ² and developed for 39 seconds. The panel was measured for remaining resist and etched according to Method 6 for residue.
The results are summarized in Table 2.

[0057]

[Table 2] Weight loss vs. development time 1 layer Coating exposure (mj / cm ² ) Development time (sec) Residual resist (micron) Residual copper 500 58 1.6 Yes 500 77 1.3 Yes 500 100 1.3 Yes 500 200 1.2 Yes 500 400 1.1 Yes 1000 39 2.2 Yes 0 39 3.0 Yes 0 58 2.8 Yes 0 77 2.6 Yes 0 100 2.7 Yes 0 200 1.7 1.7 Yes 0 400 1.4 available

The remaining thickness eventually reached the level seen in the two-layer coating developed in Example 1, but showed the presence of etch-retarded resist residues, with no cleanly etched panels. This is despite the fact that the photoactive resist coating thickness was approximately equal in the two tests, and the comparative panel was developed four times longer than that of the example.

Claims (28)

[Claims] 1. An (a) electrically conductive article; (b) a water-dispersible, non-photosensitive layer containing an acid- or alkali-soluble resin having an acid value of 20 to 300; and (c) an optical image. A formable electrodeposited layer; a photosensitive electrodeposited article substantially free of development and etch residues. 2. A photoimageable electrodeposited layer comprising: (1) a water soluble or water dispersible resin having an acid number of 20 to 300 and a number average molecular weight of at least 2000; and (2) initiation. 2. The photosensitive electrodeposition-coated article according to claim 1, which is electrodeposited from a positively-charged electrodeposition coating composition comprising an agent or an initiating system. 3. A photoimageable electrodeposited layer is a polymeric material having (a) (1) acid labile side groups and (2) free acid groups. Is 25 ~
An electrodeposition from a positive electrodeposition coating composition comprising: an acid number of 300 and a number average molecular weight of at least 2000; and (b) a substance that forms an acid upon exposure to actinic radiation.
The light-sensitive electrodeposition-coated article as described. 4. The electrodeposited layer comprises: (1) a water-soluble or water-dispersible polymerizable resin having an acid number of 20 to 300 and a number average molecular weight of not less than 300, provided that the resin is unsaturated. 150 to 30 in some cases
A negative electrodeposition coating composition having an unsaturated equivalent of 00 and used in combination with an ethylenically unsaturated compound when the resin is saturated; and (2) an initiator or an initiator system; The photosensitive electro-deposited article of claim 1 which is electro-deposited from. 5. The photosensitive electrodeposition-coated article according to claim 4, wherein a water-soluble or water-dispersible polymerizable unsaturated resin is used in combination with an ethylenically unsaturated compound. 6. The photosensitive electrodeposition-coated article according to claim 4, wherein the ethylenically unsaturated compound is a (meth) acrylic monomer. 7. The photosensitive electrodeposition-coated article according to claim 1, wherein the water-dispersible acid or alkali-soluble resin having an acid value of 20 to 300 is an acrylic polymer. 8. The photosensitive electrodeposition-coated article according to claim 4, wherein the water-soluble or water-dispersible polymerizable unsaturated resin has an acid value of 50 to 70. 9. The photosensitive electrodeposition-coated article according to claim 4, wherein the water-soluble or water-dispersible polymerizable unsaturated resin has a glass transition temperature of 0 to 100 ° C. 10. The initiator is a diazoquinone derivative,
The photosensitive, electrodeposition-coated article according to claim 2. 11. An initiator is 0.1 per 100 parts by weight of a water-soluble or water-dispersible polymerizable unsaturated or saturated resin.
The photosensitive electrodeposited article of claim 2 present in an amount of about 15 parts by weight. 12. A photoimageable electrocoat layer 5
The photosensitive electrodeposited article of claim 1 having a thickness of -100 μm. 13. The photosensitive electrodeposition-coated article according to claim 1, wherein the non-photosensitive layer has a thickness of 1-10 μm. 14. A process of: (a) applying a non-photosensitive layer containing a water-dispersible acid- or alkali-soluble resin having an acid value of 20 to 300 onto an electrically conductive article, and the following steps: (B) dipping an electrically conductive article having a non-photosensitive layer thereon in a photoimageable electrodeposition coating composition; and (c) non-photosensitive by supplying electrical current to the article as an anode. Forming an electrodeposited layer on the surface of the electrically conductive layer; comprising the steps of: electrodepositing a coated film on an electrically conductive article. 15. A photoimageable electrodeposited layer comprising: (1) a water soluble or water dispersible resin having an acid number of 20 to 300 and a number average molecular weight of at least 2000; and (2) initiation. 15. The photosensitive electrodeposited article of claim 14, which is electrodeposited from a positive electrodeposition coating composition comprising an agent or initiating system. 16. A photoimageable electrodeposited layer is a polymeric material having (a) (1) acid labile side groups and (2) free acid groups. Having an acid number of at least 25-300 and a number average molecular weight of at least 2000; and (b) a substance that forms an acid upon exposure to actinic radiation; electrodeposited from a positive electrodeposition coating composition. , Claim 1
4. The photosensitive electrodeposition-coated article according to item 4. 17. An electrodeposited layer comprising: (1) a water-soluble or water-dispersible polymerizable resin having an acid number of 20 to 300 and a number average molecular weight not less than 300, provided that the resin is unsaturated. 150 to 30 in some cases
A negative electrodeposition coating composition having an unsaturated equivalent of 00 and used in combination with an ethylenically unsaturated compound when the resin is saturated; and (2) an initiator or an initiator system; 15. The photosensitive electrodeposited article of claim 14, which is electrodeposited from. 18. The method according to claim 17, wherein the water-soluble or water-dispersible polymerizable unsaturated resin is used in combination with an ethylenically unsaturated compound. 19. The method according to claim 17, wherein the ethylenically unsaturated compound is a (meth) acrylic monomer. 20. The method according to claim 17, wherein the water-soluble or water-dispersible polymerizable unsaturated resin has a glass transition temperature of 0 to 100 ° C. 21. The initiator is a diazoquinone derivative,
The method of claim 15. 22. The initiator is 0.1 parts by weight per 100 parts by weight of a water-soluble or water-dispersible polymerizable unsaturated or saturated resin.
18. The method of claim 17, which is present in an amount of 1 to 15 parts by weight. 23. The concentration of the photoimageable electrodeposition coating composition is 3 to 25% by weight based on the non-volatile matter.
7. The method according to 7. 24. The method of claim 14, wherein the electrical current to the article is provided for 5 seconds to 5 minutes. 25. The method according to claim 14, wherein the non-photosensitive layer has a thickness of 1-10 μm. 26. Five photoimageable electrodeposition coated layers
15. The method of claim 14 having a thickness of ~ 100 [mu]. 27. The method of claim 14, wherein the non-photosensitive layer is dip coated on the electrically conductive article. 28. The method of claim 14, wherein the non-photosensitive layer is electrodeposited on the electrically conductive article.