JPH02289607A - Crosslinking, hardening resin composition - Google Patents

Abstract

PURPOSE:To provide the subject resin composition capable of being developed with an alkali aqueous solution and useful for photoresists, etc., by comprising a copolymer of methacrylic acid, styrene, methyl acrylate, methyl methacrylate, etc., a crosslinkable monomer and a photo-polymerization. CONSTITUTION:The objective resin composition comprises (A) 40-70 pts.wt. of a thermoplastic polymer for binders, prepared by copolymerizing 15-35wt.% of the first polymerizable substance such as an alpha,beta-3-15C unsaturated carboxyl group-containing monomer, 2-25wt.% of the second polymerizable substance such as a compound of formula I (R1 is H, 1-6C alkyl, etc.) or a ring-substituted derivative thereof, 10-40wt.% of the third polymerizable substance such as a 1-8C alkyl acrylate or a 2-8C hydroxyalkyl acrylate and 30-65wt.% of the fourth polymerizable substance such as a 1-8C alkyl methacrylate or a 2-8C hydroxyalkyl methacrylate, (B) 25-50 pts.wt. of crosslinkable monomers containing 51-100wt.% of a compound of formula II (R2 is 3-6C alkylene; R3 and R4 are H or CH3; n is 5-9) and (C) 0-10 pts.wt. of a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a photopolymerizable or radiation polymerizable resin composition that can be developed with an alkaline aqueous solution. [Prior Art] In recent years, so-called dry film resists having a structure in which a photopolymerizable resin layer is sandwiched between a supporting film and a protective film in a sandwich-like structure have been widely used as photoresists for producing printed wiring boards. As a photopolymerizable resin layer, there are two known types: a solvent development type in which the unexposed areas are developed and removed with a chlorine thread organic solvent, and an alkali development type in which the unexposed areas are developed and removed with an alkaline aqueous solution, but these have no effect on W1 magic. Also, alkali-developable dry film resists are becoming mainstream due to their advantage in IM production cost.

To use an alkali-developable dry film resist having a protective film and a support film, first, while peeling off the protective film from the dry film resist, the photopolymerizable resin surface is laminated with a copper clad laminate using K heat. In step (b), photocool is applied closely to the support film surface of the resist film, and the portions requiring hardening are exposed to ultraviolet rays or the like and hardened. Next, after peeling off the support film, the unexposed areas are developed and removed using a weak alkaline aqueous solution such as sodium carbonate to obtain a resist circuit pattern. Thereafter, in the case of the copper through-hole method, after etching the copper surface, the hardened resist is peeled off using a strong alkaline aqueous solution K such as sodium hydroxide to obtain a printed wiring board. In addition, in the case of the solder through hole method,
After performing copper plating and solder plating, the hardened resist is peeled off with a strong alkaline aqueous solution, and the exposed copper is further etched to obtain a printed wiring board.

During the above process, it goes without saying that the dry film resist must have sufficient resistance as an etching resist or plating resist, and up until now, various methods have been used mainly to improve this resistance. Considerations have been made.

However, many conventional alkaline-developed dry film resists have the disadvantage that the time required to peel off the hardened resist with a strong alkaline aqueous solution (peeling time) is long. If the peeling time is long, the copper surface of the board will be oxidized and discolored by the alkali K, which will not only adversely affect subsequent steps such as etching, but also, in the case of the solder through-hole method, the solder will be dissolved by the strong alkaline aqueous solution. m of the pattern during the etching process
In some cases, wire breakage or disconnection may occur, or fusing may not be possible. On the other hand, among conventional alkaline-developed dry film resists, the peeling time is short, and the hardened resist peeling pieces peeled off with a strong alkaline peeling plate have the disadvantage of being easily dissolved in the peeling solution. Ta. If the hardened resist peeling pieces are easily dissolved in the stripping solution, they easily swell and become gel-like while staying in the peeling tank.
This gel-like substance frequently clogs the filters provided in the peeler for collecting peeled pieces.

As a result, the circulation of the stripping solution may be reduced, making it impossible to strip the cured resist, or the stripping solution may overflow from the stripping tank and contaminate the area around the tank.

Furthermore, among conventional alkali-developed dry film resists that require a short peeling time, the size of peeled pieces of the cured resist that are peeled off with a strong alkaline stripping solution is too large. Some b had the drawback of being too small. If the peeled piece was too large (45 mm square), the peeled piece could become entangled with the conveyance roller of the automatic peeling machine, causing a trouble in the machine. For this reason, JP-A-64-
In Japanese Patent No. 10235, an attempt was made to reduce the size of the peeled pieces into small pieces by using a specific crosslinking monomer, but if the peeled pieces were fine ((2 sm square)
Since the peeling pieces can easily pass through the mesh of the filter for collecting peeled pieces installed in the peeler, the peeled pieces can enter the liquid circulation bomb or spray nozzle and obstruct the circulation of the peeling liquid, or the peeling liquid cannot be removed without being removed. Due to the peeling pieces staying inside for a long time, the peeling liquid deteriorates rapidly and the peeling pieces dissolve, making it necessary to frequently replace the liquid.

Furthermore, conventional dry film resists cannot simultaneously satisfy the requirements of a short peeling time, an appropriate size of peeled pieces, and insolubility of the peeled pieces in the stripping solution.

[Problem that the invention seeks to solve]

The object of the present invention is to overcome the above-mentioned drawbacks and shorten the peeling time.
The object of the present invention is to provide an alkali-developable photopolymerizable or radiation polymerizable crosslinkable resin composition in which peelable pieces have an appropriate size and are not easily dissolved in a peeling solution.

[Means to solve the problem]

As a result of intensive study by the present inventors to achieve the above object,
The inventors have discovered that these objects can be achieved by using the following photopolymerizable resin composition, and have completed the present invention.

That is, the present invention provides: (a) 15 to 35% by weight of a first polymerizable substance comprising one or more compounds of α,β monounsaturated monomers having 3 to 15 carbon atoms; , one selected from the group consisting of compounds represented by general formula (1) (wherein R is H, an alkyl group having 1 to 6 carbon atoms, or a halogen atom) and ring-substituted rust conductors thereof; or 2 to 25% by weight of a second polymerizable substance consisting of more compounds.
, a third compound consisting of one or more compounds selected from the group consisting of alkyl acrylates in which the alkyl group has 1 to 8 carbon atoms and hydroxyalkyl acrylates in which the hydroxyalkyl group has 2 to 8 carbon atoms. One or more polymerizable substances selected from the group consisting of 10 to 40 polymeric f4, alkyl methacrylates in which the alkyl group has 1 to 8 carbon atoms, and hydroxyalkyl methacrylates in which the hydroxyalkyl group has 2 to 8 carbon atoms. 40 to 70 parts by weight of a thermoplastic polymer for a binder obtained by copolymerizing 30 to 65 parts by weight of a fourth polymerizable substance consisting of the above compound, (b) General formula [■] (In the formula, R is the number of carbon atoms. 3 to 6 alkylene groups, R3 and R4 are H or OH, and n is 5 to 9
(a positive integer such as ) A crosslinked curable resin composition in which 0 to 10 parts by weight of a photopolymerization initiator are combined in a total amount of 100 parts by weight.

The thermoplastic polymer for the binder constituting the crosslinkable resin composition of the present invention contains an α,β-monomer having 3 to 15 carbon atoms so that it can be developed with a dilute alkali aqueous solution such as sodium carbonate. It is necessary to copolymerize one or more saturated carboxyl group-containing monomers as the first polymerizable substance in a proportion of 15 to 35% by weight. Examples of carboxylic acid type monomers that may be used include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorpic acid, itaconic acid, propiolic acid, maleic acid and fumaric acid, and Esters or anhydrides can also be used. The most preferred compounds among these are acrylic acid and methacrylic acid. These carboxylic acid type components are desirably used so that the content in the copolymer is 15 to 35% by weight, preferably 18 to 30% by weight.Carboxylic acid component content in the copolymer If the amount of copolymerized carboxylic acid is less than 15% by weight, it cannot be developed with an alkaline aqueous solution or the development time will be too long, resulting in a decrease in resolution.On the other hand, if the amount of copolymerized carboxylic acid is less than 35%
If the amount exceeds 11i, the development time will be too short, making it difficult to control the development while obtaining a high-resolution pattern, and the water resistance of the cured portion will also decrease.

The second polymerizable substance to be copolymerized into the binder resin has the general formula [1] R, -0-OH (where R1 is H, an alkyl group having 1 to 6 carbon atoms, or a halogen atom). ) is a compound represented by The benzene ring of the substance is a functional group such as a nitro group, an alkoxy group, an alkyl group, a carboxyl group, a sulfone group, or a hydroxyl group, such as a halogen.
It may be detected, and the substituted residue of the benzene nucleus is 1 to
It may be in the range of 5. I like it. The Ln substituent is a single alkyl group, such as a methyl or t-butyl group. The most preferred of these compounds is styrene. These second polymerizable components need to be κ-copolymerized so that the thermoplastic copolymer for the binder has a weight range of 2 to 25, preferably 3 to 20 weight. If the copolymerization amount of this component is less than 2% by weight, it will not be possible to obtain a resist material with excellent chemical resistance, especially plating resistance. The resist resin layer of the dry film resist is too hard and the resist d! Peeling tends to occur, and the time required for development and peeling increases.

The third polymerizable substance that may be contained in the binder resin is an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 8 carbon atoms. Examples of these compounds include methyl acrylate, ethyl acrylate, n-propylacrylate, iso-propylacrylate, n-butyl acrylate, sea-
Examples include butyl acrylate, t-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, and 2-ethylhexyl acrylate. The most preferred of these compounds are methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. These acrylate-type components add 10 to 40
It is necessary to carry out copolymerization so that the weight percent is preferably in the range of 15 to 55 weights -@4. If the content number of the acrylate type component is less than 10 times - 1'14, a dry film resist with sufficient flexibility cannot be obtained, resulting in poor adhesion to the base material and embedding of the resist resin into irregularities on the surface of the base material. The plating resistance of the resist decreases due to insufficient properties. On the other hand, if the copolymerization amount of the third polymerizable substance exceeds 40% by weight, the resist resin is too soft and when the resulting dry film resist is wound into a roll and stored, the resist resin is stuck between the supporting film. This causes the so-called cold flow phenomenon that oozes out over time.

The fourth polymerizable substance copolymerized in the binder resin is copolymerized in combination with alkyl acrylate or hydroxyalkyl acrylate to give an appropriate glass transition temperature (Tg) to the thermoplastic polymer for the binder. These are alkyl methacrylates having an alkyl group having 1 to B atoms and hydroxyalkyl methacrylates having a hydroxyalkyl group having 2 to 8 carbon atoms. Examples of these compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, 18o-propyl methacrylate, n-butyl methacrylate, BeC-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxy Examples include glopyl methacrylate, 2-ethylhexyl methacrylate, and the like. The most preferred of these compounds is methyl methacrylate.

These methacrylate components need to be copolymerized in a range of 30 to 65% by weight, preferably 65 to 60% by weight, in the thermoplastic copolymer for binder.

In order to achieve the object of the present invention, the thermoplastic polymer for the binder used in the present invention needs to be a polymer composed of the above-mentioned specific monomers, and has a weight average molecular weight of 4G,000 to 50G. ,000 range is desirable. When a dry film resist with a weight average molecular weight of less than 40,000 is used, it tends to cause the K cold flow phenomenon, and those with an inverse K weight average molecular weight of more than 40,000 may be dissolved in an alkaline developer in the unexposed area. The development property is poor, and the development time is extremely long, resulting in a decrease in resolution and productivity of circuit patterns.

The thermoplastic polymer for binder used in the present invention is contained in 40 to 70 parts by weight, preferably 45 to 65 parts by weight, in 100 parts by weight of the photopolymerizable resin composition. If the photopolymerizable resin composition contains less than 40 parts by weight of the thermoplastic polymer for the binder, the film forming properties of the photosensitive layer of the obtained dry film resist will be impaired, sufficient film strength will not be obtained, and cold claw will occur. Cheap. On the other hand, if the content of the thermoplastic polymer exceeds 70 parts by weight, the photocured film will be brittle.
Adhesion to the base material is impaired, and sufficient chemical resistance, particularly plating resistance and etching resistance, cannot be obtained.

The crosslinkable monomer comprising one or more compounds having one or more ethylenically unsaturated groups in one molecule constituting the composition of the present invention contains the general formula [11] O O (formula Medium RsFi is an alkylene group having 3 to 6 carbon atoms, R3 and R4 are H or CUS, and n is n=
It is essential to contain 51 to 100 weight percent of the compound represented by (a positive integer such as 5 to 9), preferably 55 to 90 weight percent. The content of the compound is 5
In a dry film resist obtained using a cross-linkable monomer with a molecular weight of less than 1, as the peeling time of the cured resist with the alkaline aqueous solution K increases, the peeling pieces become extremely easy to dissolve in the stripping solution, and the peeling pieces become difficult to dissolve. It becomes difficult to control the size to an appropriate size.

In formula (n), R! is an alkylene group having 3 to 6 carbon atoms. When a crosslinkable resin composition made using a compound in which R1 has 2 or less carbon atoms, such as polyethylene glycol diacrylate, is cured, the crosslinking density increases so much that not only does the peeling time become longer, but also Since the hydrophilicity of the crosslinkable monomer becomes high, the peeled pieces of the cured resist become too fine and are easily dissolved in the peeled MI&, so it is preferable that R2 has 7 or more carbon atoms. On the contrary, a crosslinkable resin composition prepared using the compound described above is not preferable because it has insufficient curability and chemical resistance, particularly plating resistance and etching resistance, decreases.

In the formula [■], ntin is a positive integer from 5 to 9. When a crosslinkable resin composition made using a compound in which n is 4 or less is cured, the crosslink density increases so much that not only does the peeling time become shorter, but also the peeled pieces of the cured resist become opaque. If it is too thick, it will easily pass through the filter mesh of the peeling machine, which is undesirable. On the other hand, cross-linked resin compositions made using materials with n of 10 or more have insufficient curability, resulting in poor chemical resistance, especially plating resistance and etching resistance, as well as excessively large peeling pieces. This is undesirable because it gets tangled with the conveyance roller of the peeling machine.

Therefore, in order to obtain a crosslinkable resin composition that simultaneously satisfies the objectives of the present invention, such as good chemical resistance, excellent peelability, non-dissolubility of peelable pieces, and appropriate size of peelable pieces, in formula [B], R, is an alkylene group having 3 to 6 carbon atoms, and n must be in the range 5 to 9.

As a compound represented by the formula [■], hexer 1.3-
Propanediol di(meth)acrylate (hexa is [■
] In the formula, n = 6, 1,3-propanediol is R2== -OH,OH,OH2-, and (meth)acrylate is R,,R4=H
or aH. The same applies to the following expressions), octa-1,3-propanediol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, hexapropylene glycol di(meth)acrylate, octapropylene glycol di(meth)acrylate, Nonar 1,2-butanediol di(meth)acrylate, Tetra 1,5-butanediol di(meth)acrylate, Hexer 1,3-butanediol di(
meth)acrylate, octa 1,3-butanediol di(meth)acrylate, venter 1,4-butanediol di(meth)acrylate, nonar 2,3-butanediol di(meth)acrylate, venter 2-methyl-
1.3-propanediol di(meth)acrylate, hepta-2-methyl-1.3-propanediol di(meth)acrylate, nonar 2-methyl-1.5-propanediol di(meth)acrylate, hepta-1 .1-dimethyl-1,2-ethanediol di(meth)acrylate, octa 1,2-pentanediol di(meth)acrylate, nonar 1,3-pentanediol di(meth)acrylate
Acrylate, hexar 1,4-pentanediol di(
meth)acrylate, hepta-1,5-bentanediol di(meth)acrylate, octa-2,3-pentanediol di(meth)acrylate, hepta-2,4-pentanediol di(meth)acrylate, Tetra 2.
2-dimethyl-1,3-propanediol di(meth)acrylate, hexer 2,2-dimethyl-1,3-propanediol di(meth)acrylate, octa-otsu2-
Dimethyl-1,3-propanediol di(meth)acrylate, octa-1,2-hexanediol di(meth)
Acrylate, hexar 1,3-hexanediol di(
meth)acrylate, Hep J-1,4-hexanediol di(meth)acrylate, Venter 1,5-hexanediol di(meth)acrylate, Tetler 1,
6-hexanediol di(meth)acrylate, hepta-1,6-hexanediol di(meth)acrylate,
Octa 2,3-hexanediol di(meth)acrylate, Nonar 2,4-hexanediol di(meth)acrylate, Hepta-2,5-hexanediol di(meth)acrylate, Hexer 44-hexanediol di(meth)acrylate,
Examples include meth)acrylate. Among the preferred compounds R, the following general formula ([11] (where R3 and R4 are FiH or OH3, and n is n
pentabrobylene II cold di(meth)acrylate, hexapropylene glycol di(meth)acrylate, heptapropylene glycol di(meth)acrylate, octapropylene glycol di( meth)acrylate, nonapropylene glycol di(meth)acrylate, and as a commercially available product, for example, NK monoester 9 pG%
Examples include NK monoester APG-400 (both manufactured by Shin-Nakamura Chemical Industry ■). A more preferred compound is heptapropylene glycol di(meth)acrylate in formula (III) where n=7, and commercially available products include, for example, NK-ester APG-400 (manufactured by Shin Nakamura Chemical Industry ■). There is. These may be used alone, but two or more types may be used in combination. Any compound can be used as long as it has at least 1 ethylenically unsaturated group, examples of which include phenoxydiethoxy(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, .6-hexanediol di(meth)acrylate, neobentylglycol di(meth)acrylate, 2.2-bisC4-(meth)
Acrylo, xypolyethoxyphenyl]broban, 2.
2-bis[4-(meth)acryloxypolypropyleneoxyphenyl]propane, hydroxybivalic acid neobentylglycol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolethane di (meth)acrylate, trimethylolethane tri(meth)acrylate,
Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tris [polyethoxy(meth)acrylate], trimethylolpropane tris [polypropyleneoxy(meth)acrylate 1 isocyanuric acid triethyl di(meth)acrylate] Acrylate, triethyl isocyanurate tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, diventaerythritol tetra( meth)acrylate, diventaerythritol benta(meth)acrylate, diventaerythritol hexa(meth)acrylate, compounds with formula (n) where n=1 to 4, polyvalent compounds exclusively for compounds with formula (n) where n is 10 or more Alcohol (meth)acrylates, acrylamide derivatives such as n-putokyV methylacrylamide, 1eO-putokyV methylacrylamide, epoxy (meth)acrylates, and urethane (meth)acrylates, etc., may be used singly or in combination. You can use it, or you don't have to.

In order to impart to the photopolymerizable resin composition of the present invention the excellent easy peelability of a cured resist, an appropriate peelable piece size, and the insolubility of the peelable pieces in an alkaline solution, which are the objects of the present invention, the above-mentioned Specific thermoplastic polymer for binder 40-70
It is essential to use 25 to 50 parts by weight of a crosslinkable monomer represented by formula (II) in a specific amount based on the weight part, and the composition is outside the scope of the present invention. However, it is not possible to obtain a dry film resist that simultaneously achieves the objects of the present invention, such as excellent easy peelability, appropriate peelable piece size, and peelable piece insolubility. As described above, the thermoplastic polymer used in the present invention enables resist development and stripping with an alkaline aqueous solution by using a specific amount of a carboxylic acid type monomer as a copolymerization component. By blending the bridging monomer represented by above in a specific amount or more with these thermoplastic polymers, it is possible to achieve unexpectedly excellent peelability, appropriate peeling piece size, and peeling piece insolubility. This made it possible to create a dry film resist that could express the following.

Although the detailed mechanism of K has not been fully elucidated, the formula (I
By using the crosslinkable monomer represented by I), the photopolymerizable resin composition is moderately cured, and due to the moderate hydrophilicity of the crosslinkable monomer (11), the cured resist is cured in an alkaline aqueous solution K. Therefore, it is expected that the non-uniformity of the swelling pressure during swelling increases, so that the ease of peeling improves, and that the cured resist peels off with appropriate size κ cracks.

Moreover, it is thought that because the molecular structure of this crosslinking monomer (II) is moderately hydrophobic, the solubility in the aqueous κ alkali solution is reduced, and the peeled pieces become insoluble.

The crosslinking monomer having an ethylenically unsaturated group used in the present invention K is contained in 25 to 50 parts by weight, preferably 30 to 45 parts by weight in 100 parts by weight of the crosslinkable resin composition of the present invention. If the content of the crosslinkable monomer is less than 25 parts by weight, the photopolymerizable composition will not be sufficiently cured by light.
Chemical resistance, special K plating resistance, and etching resistance decrease,
On the other hand, if a dry film resist with a content of more than 50 parts by weight of the crosslinkable monomer is used, cold flow is likely to occur, and the easy releasability of the photocured product with an aqueous alkaline solution K is reduced. do.

The photopolymerization initiators used when photopolymerizing the crosslinkable resin composition of the present invention include penzophenone, Michler's ketone, 4,4'-pis(diethylamino)penzophenone,
t-butylanthraquinone, 2-ethylanthraquinone, thioxanthones, penzoin alkyl ethers,
Known ones such as pendyl ketals can be used,
One or more of these can be used in combination.

When the photopolymerization initiator used in the present invention is cured with ultraviolet rays, the photopolymerization initiator (
Li to 10 parts by weight is contained.

If it is less than 1 part by weight, the resulting crosslinkable resin composition will not be sufficiently photocured, while if it exceeds 10 parts by weight, it will become thermally unstable. In addition, when the crosslinkable resin composition of the present invention is cured with an electron beam, the photopolymerization initiator may not be included.b6 The crosslinkable resin composition of the present invention has even higher plating resistance. It is preferable to contain k-tetrazole or a derivative thereof in order to improve the performance. Tetrazole or its derivatives can improve adhesion to metal surfaces by adding small amounts; examples include 1-phenyltetrazole and 5-phenyltetrazole.
17-enyltetrazole, 5-7 minotetrazole, 5
-amino-1-methyltetrazole, 5-amino-2-
Examples include phenyltetrazole, 5-mercapto-1-phenyltetrazole, 5-mercapto-1-methyltetrazole, and one or more of these can be used in combination. Compounds other than the above-mentioned tetrazoles, such as benzo, IJ azole, penzimidazole, etc., improve the plating resistance.K has excellent effects unless used in large amounts.
On the other hand, when used in large amounts, these compounds not only reduce the sensitivity of the crosslinkable resin composition of the present invention, but also remain on the copper surface even after development or peeling, impairing plating adhesion or delaying etching. This is not desirable because it can cause

The amount of tetrazole or its derivative used is preferably in the range of 5 to 5 parts by weight (LOO5 to 5 parts by weight), based on the total of 100 parts by weight of the thermoplastic polymer for binder, crosslinkable monomer, and photopolymerization initiator.α005 parts by weight If it is less than 5 parts by weight, no clear improvement in plating resistance will be observed, while if it exceeds 5 parts by weight, it will take a long time to dissolve into the crosslinkable resin composition, and the sensitivity of the crosslinkable resin composition will also decrease.

Components such as a thermal polymerization inhibitor, a dye, a plasticizer, and a filler may be added to the crosslinkable resin composition of the present invention, if necessary.

The crosslinkable resin composition of the present invention can be directly formed into a film on the target substrate even in the absence of a diluent, but solvents with a not very high boiling point, such as acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, dichloromethane, etc. , chloroform, methyl alcohol, ethyl alcohol, isopropyl alcohol, etc., are dissolved and mixed in 1 mt or more, and it is easy to form a hexagonal film.

The amount of these solvents used is 200 parts by weight or less, preferably 50 to 150 parts by weight, based on 100 parts by weight of the crosslinkable resin composition.

In addition, in order to form a dry film resist using the crosslinkable resin composition of the present invention, a blade coater, a rod coater, a knife coater, a roll tractor coater, a comma coater, a J bar roll coater, a transfer roll coater, a clarifier coater, a kiss roll coater are used.
It can be applied using a curtain coater etc.
When a solvent is used in the composition, it is necessary to scatter the solvent. A plastic film such as polyester is mainly used as the support. When using a flammable organic solvent as a dryer, use a dryer equipped with an air-heating heat source using steam for safety reasons, and use a method that brings the hot air inside the dryer into countercurrent contact and blows it onto the support from a nozzle. method etc. are used. The shape of the dryer is selected depending on the purpose, such as an arch type or a flat type.

If necessary, the dry film resist after drying may be laminated with a protective film such as polyethylene or polypropylene.

The dry film resist produced as described above has extremely good peelability, peelable piece size, and peelable piece insolubility, and has excellent workability and process passability as an etching and plating resist, and can produce high-resolution patterns. It will be done.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

Synthesis Example 1000 m four-necked flask K1 equipped with nitrogen inlet, stirrer, condenser and thermometer Isobrobyl alcohol 100 ml under nitrogen atmosphere. , methyl ethyl ketone 10
0t and 200f of a monomer having the composition shown in Table 1 were added, and the temperature of the water bath was raised to 80° C. without stirring. Then azobisisobutyronitrile 1. (1 of D4 was dissolved in sopropyl alcohol and polymerized for 4 hours. Then, 1 of azobisisobutyronitrile was added to 10
The mixture was dissolved in isopropyl alcohol of 100 g and added in 5 portions at 30 minute intervals, and then the internal temperature of the flask was raised to the freezing point of the solvent and polymerization was carried out at that temperature for 2 hours. After the polymerization was completed, 100 t of isopropyl alcohol was added, the polymerization reaction product was taken out from the flask, and the binder resin solution was
11 to obtain binder resin solutions ▲ to P shown in Table 1K. In addition, the polymerization rate Fi of the monomer mixture in each composition
Both are 9 9. It was 5'1 or more. The solid content in the binder resin solution was 3a7 weight range in all cases.

Examples 1 to 11, Comparative Examples 1 to 14 Using the binder resin solution A-IF obtained in the synthesis example,
A photopolymerizable resin composition having the composition No. 2 was prepared.

The prepared composition was stirred with a propeller type mixer and coated with a blade coater onto a polyester film having a thickness of 25 μm and a width of 560 mm to a coating width of 540 m. Next, hot air was sent in a countercurrent flow through a dryer having a height of 100 cm and a length of 8 m for 400 days to obtain a dry coating thickness of 50 μm.

The coating speed at this time was 5 m/min, and the hot air temperature was 90°C. Next, a polyethylene protective film with a thickness of 55 μm was laminated on the dried coating film, and then
It was wound into a roll to a length of m. This roll was placed horizontally in a constant temperature room at 25°C for 5 days, and the state of the cold flow from the end of the roll was visually observed.The results are shown in the table below.
Shown in 3.

The obtained dry film resist was heat laminated on the copper clad laminate while removing the protective film, and after the temperature of the copper clad laminate returned to room temperature, the photosol was adhered to the polyester film surface. It was then exposed to light using an ultra-high pressure mercury lamp. The ultra-high pressure mercury lamp uses Ushio Inc. UgH-102D.
100 mJ/one irradiation was performed. At this time, the exposure intensity was measured using the Ushio Inc. ultraviolet intensity meter U-T-100 and the receiver DVD-
365P was attached and measured, and it was set to 5 mwZ-16
'iK After exposure, leave for 20 minutes and peel off the support film.
Developed with a sodium 4 carbonate + 3 um aqueous solution. Develop at liquid temperature 3
0℃, spray pressure takg/mouth! The distance between the binding and the spray and the substrate was set at 10 times. Next, after degreasing by immersing in a neutral degreaser for about 1 minute at room temperature, spray washing in an overflow tank for about 1 minute, then immersing it in a 20 part ammonium persulfate aqueous solution for 1 minute, and spray washing again for about 1 minute. I did it.

Thereafter, it was immersed in 10 drops of sulfuric acid for 1 minute, and then sprayed and washed with water for 1 minute again. Next, after 1 minute immersion in 10% sulfuric acid, immersion in copper sulfate plating solution κ, 2. SA/dm" is 75
Steel plating was performed for minutes. The liquid temperature at this time was 22°C. Immediately after plating, the plate was washed with water, immersed in a 15% borohydrofluoric acid aqueous solution for 1 minute, and then immersed in a high-speed solder plating solution.1. Solder plating was performed for 18 minutes at 8 a/am''.The liquid temperature at this time was 22°C.After plating was completed, it was washed with water and then dried.Table 3 shows the plating resistance of each dry film resist. The compositions of the copper plating solution and the solder plating solution are as follows.

(Steel plating solution) Sulfuric acid steel 98 Sulfuric acid 36eII Hydrochloric acid brightener (Solder plating solution) Tin 1 5 Ta/L Lead
109/t free borohydrofluoric acid 4
0 0 9/t Free boric acid 21.6 t/L Bepton S2 ta/t Using the sample after solder plating, remove the resist with a 5-width sodium hydroxide aqueous solution at 45°C 7 5 t/L 1 9 0 ta /t (L 1 2mg/t 5d./t. Peeling was performed by increasing the distance between the sample and the spray nozzle by 10
3, spray pressure 1. It was carried out at 0 k9/t.

The time required to peel off the resist at this time and the size of the peeled pieces were measured, and the results are also shown in Table 5.

After peeling evaluation, the peeled pieces were collected, placed in a beaker containing an aqueous solution of 34-sodium hydroxide, sealed, kept at 45°C for 24 hours using a constant temperature water bath, and visually observed to see if the peeled pieces had dissolved. The results are also shown in Table 3K.

Table-1 (Note) The solid content of the binder resin solution is also 3 & 7.
weight, therefore 100 parts by weight of binder resin solution, 12
The solid contents in 0 parts by weight, 150 parts by weight, 165 parts by weight and 185 parts by weight are respectively 3 & 7 parts by weight, 464 parts by weight, SaO parts by weight, 6 & 9 parts by weight and 71.6 parts by weight*1. Product Name: BIK Ester AP (}-400 (Shin Nakamura Chemical Industry ■) *2 Product Name: uK Ester ▲-400 (Shin Nakamura Chemical Industry ■IB) *5 Product Name: IJK Ester ▲ PG-200 (Shin Nakamura Chemical Industry ■) Table 3 (#!ki) (Note 1) Plating resistance 0: Very good ○: Good ∆~○: Slightly less plating: Too much plating X~∆: Plating between patterns With bridge ×
: Many plated bridges between patterns (Note 2) Large size of detached pieces :〉 4 5 fin angle Medium: 3 to 4 0 ■ fin angle Small: (2 m square [Effect of the invention] As detailed above, K, By using the crosslinkable resin composition of the present invention in Dry Film K, it is possible to exhibit the characteristics that the peeling time is short, the peelable pieces have an appropriate size, and the peelable pieces do not easily dissolve in the stripping solution. Then,
As a result, problems such as discoloration of the copper surface caused by Alka-13K, peeling pieces getting entangled with the conveyor roller of the desoldering machine, rapid deterioration of the stripping solution, and clogging of the peeling machine's filter are eliminated, and productivity is increased. Therefore, its industrial value is extremely large.

Procedural amendment January 9, 1990

Claims (1)

[Claims] 1. (a) A first polymerizable substance 15-35 comprising one or more compounds of α,β-unsaturated carboxyl group-containing monomers having 3 to 15 carbon atoms. Compounds represented by weight%, general formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (wherein R_1 is H, an alkyl group having 1 to 6 carbon atoms, or a halogen atom) and 2 to 25% by weight of a second polymerizable substance consisting of one or more compounds selected from the group consisting of ring-substituted derivatives thereof; an alkyl acrylate having an alkyl group of 1 to 8 carbon atoms; 10 to 40% by weight of a third polymerizable material consisting of one or more compounds selected from the group consisting of hydroxyalkyl acrylates having ~8 carbon atoms, an alkyl group having from 1 to 8 carbon atoms; A binder obtained by copolymerizing 30 to 65% by weight of a fourth polymerizable substance consisting of one or more compounds selected from the group consisting of methacrylate and hydroxyalkyl methacrylate in which the hydroxyalkyl group has 2 to 8 carbon atoms. (b) General formula [II] ▲ Numerical formula, chemical formula, table, etc. are available▼ [II] (In the formula, R_2 is an alkylene group having 3 to 6 carbon atoms, R_3 and R_4 are H or CH_3, n
is a positive integer of 5 to 9) 25 to 50% by weight of a crosslinkable monomer having one or more ethylenically unsaturated group in one molecule containing 51 to 100% by weight of the compound represented by and (c) photopolymerization initiator in a total amount of 10 to 10 parts by weight.
A cross-linked curable resin composition that is combined so as to have 0 parts by weight. 2. The crosslinkable monomer (b) having one or more ethylenically unsaturated groups in one molecule has the general formula [III]▲mathematical formula, chemical formula,
There are tables etc. ▼ [III] (In the formula, R_3 and R_4 are H or CH_3,
(n is a positive integer of 5 to 9) The crosslinked curable resin composition according to claim 1, characterized by containing 51 to 100% by weight of the compound represented by the following. 3. The crosslinked curable resin composition according to claim 2, wherein the number of oxypropylene repeating units of the compound represented by the general formula [III] is n=7. 4. Tetrazole or its derivative (a) + (b) +
(c) 0.005 to 5 parts by weight per 100 parts by weight of the crosslinked curable resin composition according to claims 1, 2, and 3.