JPH07120930A - Method for fitting cover coat and pattern forming method - Google Patents

Abstract

PURPOSE:To provide a method for fitting a cover coat by which fine image pattern forming ability is imparted to a photosensitive resist while ensuring high resolution without reducing the photosensitivity owing to oxygen and to provide a pattern forming method using the resulting cover-coated photosensitive resist. CONSTITUTION:A nonphotosensitive coating layer not practically having stickiness at ordinary temp. but having oxygen isolating property and soluble in a developer is formed on a base film to obtain a transfer film. The surface of the nonphotosensitive coating layer of this transfer film is allowed to adhere to the surface of a photosensitive coating layer having stickiness at ordinary temp. formed on a substrate, the base film is peeled off and the nonphoto- sensitive coating layer is transferred to the photosensitive coating layer to fit a cover coat. A pattern is formed using the resulting cover-coated photosensitive resist.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for mounting a photosensitive resist for pattern formation on a cover coat.
An oxygen-blocking and substantially non-adhesive non-photosensitive coating layer is formed on a supporting film, and the non-photosensitive coating layer is formed on the substrate to form an adhesive photosensitive coating layer. The present invention relates to a cover coat mounting method of a photosensitive resist for pattern formation, which is transferred onto the surface and cover-coated, and a pattern forming method using the photosensitive resist coated with the cover.

[0002]

2. Description of the Related Art As a pattern forming method for forming a circuit for electronic equipment, a pattern printing method, photolinography using a photosensitive liquid resist or a photosensitive dry film resist, etc. are known. However, in recent years, it has been difficult to obtain the required accuracy in pattern printing due to the increase in the density and thinning of patterns, and the method by photolinography is mainly used for forming fine patterns.

The dry film resist is usually composed of a light-transmissive support film, an adhesive photosensitive resin layer formed thereon, and a protective film therefor. The pattern forming method using a dry film resist is a dry film consisting of a light-transmitting support film, a photosensitive resin layer and a protective film, first, after peeling off the protective film, the photosensitive resin layer is pressure-bonded onto the substrate. , Irradiating an actinic ray through a photomask and a light-transmitting support film on which a required pattern is drawn, and then performing a developing treatment with a developing solution that selectively dissolves the unexposed portion to form a desired pattern on the substrate. Consists of forming.

Furthermore, when the substrate is an etchable material such as a copper clad laminate, it is further etched or imaged and the exposed metal such as copper is metal plated. After that, the cured resist on the substrate is peeled off with an alkaline aqueous solution or the like, and then the exposed portion is treated with an etching liquid that selectively etches, whereby an etching pattern can be formed.

However, in recent years, the density of electronic circuits has been further increased, and high resolution has been required for forming circuit patterns, and dry film resists cannot meet the requirements. Because the dry film resist is exposed through the light-transmissive support film, it is preferable that the thickness of the support film is as thin as possible in order to obtain high resolution, but the support film is coated with the photosensitive resin layer. In order to function as a support for
This is because a certain thickness, that is, a thickness of 15 to 50 μm is generally required, and it becomes difficult to obtain high resolution.

If the support film can be peeled off and exposed, the resolution can be greatly improved, but in this case, the adhesiveness of the photosensitive layer makes it easier for dirt and dust to adhere to the environment. It must be cleanly clean, and since the photosensitive layer comes into contact with oxygen, it causes a problem that the photosensitivity is significantly reduced, which makes practical application difficult.

On the other hand, although the problem of resolution is solved by using a liquid photoresist, in order to obtain a highly sensitive resist, the glass transition temperature of the uncured photosensitive resist film should be lower than room temperature and It is necessary to block oxygen from oxygen.

When the glass transition temperature of the uncured resist film is lower than room temperature, the film becomes tacky, and when contact exposure is performed using a photomask or the like, the resist film sticks to the photomask or the like during exposure, resulting in photomask or the like. Are contaminated, or the resist film is damaged, and defects such as shorts and disconnections are likely to occur in the formed resist pattern.

Further, a direct drawing method (L
When the exposure is performed by the DI method), the sensitivity is significantly lowered due to the inhibition of curing by oxygen in the atmosphere.

In order to solve these problems, a cover coat mainly composed of a water-soluble or alkali-water-soluble polymer having a glass transition temperature of room temperature or higher having a high oxygen barrier property such as polyvinyl alcohol is applied to the resist. Is being done.

These cover coats can make the resist film non-adhesive, and when applied to the LDI method or the like, the cover coat may have a film thickness capable of exhibiting a necessary oxygen barrier property. From the above, it is better to be thin, but generally, a film having a thickness of 0.5 to 5 μm is used.

However, it is generally difficult to uniformly apply a cover coat as a thin film of 0.5 to 5 μm on a highly tacky resist film, and a defect of a formed pattern due to incompleteness of the cover coat film or Contamination of the mask film is likely to occur.

[0013]

Means for Solving the Problems The inventors of the present invention have made earnest studies on a method for mounting a cover coat of a resist for pattern formation which does not have the above problems, and as a result, formed a coating layer for the cover coat on a support film. Then, it was found that a uniform cover coat can be obtained by transferring the coating layer onto the adhesive resist film, and completed the present invention.

Thus, according to the present invention, a support film and a non-photosensitive film formed thereon, which is substantially non-adhesive at room temperature, has an oxygen barrier property and is soluble in a developing solution. The non-photosensitive coating surface of the transfer film consisting of layers is adhered to the photosensitive coating layer on the substrate having the photosensitive coating layer having adhesiveness at room temperature, and then the support film is peeled off to form the non-photosensitive coating. Provided is a cover coat application method, which comprises transferring a layer to a photosensitive coating layer to form a cover coat.

According to the present invention, there is further provided a pattern forming method using a photosensitive resist cover-coated by the cover-coat mounting method.

In the present invention, the transfer film having the non-photosensitive coating layer formed on the support film may be hereinafter referred to as "cover coat transfer film". Further, the photosensitive resist which is cover-coated by the above-mentioned cover-coat mounting method may be referred to as "cover-coating resist".

Using the cover coat mounting method of the present invention,
A photosensitive resist with a cover coat, which has extremely high sensitivity, high resolution, high reliability, and excellent workability, can be easily formed on a substrate.

According to the method for forming an etching pattern using the resist with a cover coat of the present invention, first, a material on which at least one side such as a copper clad laminate can be etched is formed on a substrate on which a pattern is to be formed. After forming the above-mentioned adhesive photosensitive coating layer on the etchable surface of the substrate, the cover coat transfer film of the present invention is adhered (pressed), the supporting film is peeled off, and the cover film is peeled off on the photosensitive coating layer. After forming the cover coat layer, selectively expose,
Then, the circuit pattern and the like can be obtained by performing development, etching and the like as in the case of the conventional dry film. The selective exposure can be performed by a method known per se such as a contact exposure method using a pattern mask, a projection exposure method, a laser direct writing method.

The method of the present invention will be described in more detail below.

The support film used in the cover coat transfer film of the present invention is not particularly limited as long as it has heat resistance and solvent resistance necessary for coating and drying a non-photosensitive layer to obtain a uniform film. None, it may be transparent or opaque, for example, polyester film, nylon film, vinylidene chloride film, vinyl chloride film, polyethylene film, synthetic resin film such as polypropylene film, or a film obtained by further treating them with a release agent, Metal foil such as aluminum foil can be used.

The non-photosensitive coating layer in the cover coat transfer film of the present invention generally has a thickness in the range of 0.5 to 5 μm, preferably 1 to 3 μm, is substantially tack-free at room temperature, and contains no oxygen. It is made of a material with a blocking ability. Since the non-photosensitive coating layer is required to have substantially no tackiness, its glass transition point is 20 ° C. or higher, and further 30 ° C.
The above is preferable. However, if the glass transition point becomes too high, the film will become too hard, so
Usually, it is preferably 80 ° C or lower, and particularly preferably in the range of 40 to 70 ° C.

The oxygen barrier property of the non-photosensitive coating layer is 5 × 10 ⁻¹² cc · cm / cm ² · se as the oxygen gas permeability of the film.
c · cmHg or less, especially 1 × 10 ⁻¹² cc · cm / cm ²
It is preferably not more than sec · cmHg. Here, the oxygen gas permeability is determined by ASTM standards D-1.
It is a value measured according to the method described in 434-82 (1986).

Further, it is desirable that the non-photosensitive coating layer is one that is substantially completely dissolved in the developing solution. If it is not soluble in the developer, the cover coat must be peeled off before development, which is disadvantageous in terms of productivity. As the film-forming resin for forming the cover coat that satisfies such conditions,
For example, polyvinyl alcohol, partially saponified polyvinyl acetate or a mixture thereof, or a mixture of polyvinyl alcohol and a vinyl acetate polymer can be used. These are preferable because they are excellent in film forming property and have good solubility in an aqueous developer such as water, diluted alkaline water, diluted acid water and the like.

On the other hand, the photosensitive coating layer of the cover-coated resist of the present invention needs to be tacky at room temperature, and its glass transition point is generally 5 ° C. or lower, particularly 0 to -6.
It is preferably in the range of ° C. Further, since the photosensitive coating layer needs to be crosslinked and cured by irradiation with actinic rays,
The resin and / or additive in the photosensitive resin composition forming the photosensitive coating layer contains a photosensitive functional group which can be activated directly or indirectly by light irradiation and react to crosslink and cure.

When the photosensitive functional group in the composition is one which is indirectly activated by light, the photosensitive coating layer is
An initiator or an initiator / sensitizer (initiator system) which is activated by light and causes a reaction of a functional group is further contained.

The unexposed area of the photosensitive coating layer must be soluble in the developing solution. As the developing solution, it is usually preferable to use water or a weak alkaline or weakly acidic aqueous developing solution, but in order to develop with such an aqueous developing solution, the resin composition forming the photosensitive coating layer is A functional group such as a carboxyl group or an amino group which forms a salt capable of dissociating by the addition of about 0.5 mol to 3 mol per 1 kg of the resin, or a water-soluble onium base such as a quaternary ammonium base or a tertiary sulfonium base. 1 kg of resin such as functional groups
It is preferable to contain about 0.3 to 2 mol per unit.

Examples of the film-forming component of the composition include a resin component and a low molecular weight compound having a crosslinkable photosensitive functional group such as a multi-vinyl monomer, a low molecular weight epoxy oligomer and the like, which is optionally added.

The resin component may or may not contain a crosslinkable curable functional group itself, but as a whole film-forming component, a crosslinkable curable photosensitive functional group is generally contained per 1 kg of the film-forming component. It is important to include it within the range of 1.0 to 7 mol, preferably 2 to 5 mol. If the amount of the photosensitive functional group is less than 1 mol, the curability will be poor and the pattern formation will take a long time. If it is more than 7 mol, it will be difficult to remove the cured resist after the pattern is formed on the substrate by etching. It is easy to become.

The crosslinkable and curable photosensitive functional group is not particularly limited as long as it can be directly or indirectly activated by irradiation with actinic rays to be crosslinked and cured, and examples thereof include (meth) acryloyl group, cinnamoyl group, Examples thereof include a chalcone group, a bisazide group, an epoxy group, and the like, and a (meth) acryloyl group that can be relatively easily introduced into a resin or a low-molecular compound is particularly preferable.

As the resin component, for example, an acrylic resin, an epoxy ester resin, a polyester resin, a maleinized polybutadiene resin, a styrene-maleic anhydride copolymer resin or the like can be used.

Examples of the photocurable resin having a photosensitive functional group introduced therein include a copolymer of (meth) acrylic acid and another copolymerizable monomer, glycidyl (meth) acrylate or 3,4-epoxycyclohexyl. High acid value unsaturated acrylic resin to which (meth) acrylic acid ester of methanol is added; containing an epoxy group obtained by copolymerizing dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate and other copolymerizable monomer Acrylic resin or unsaturated acrylic resin obtained by adding (meth) acrylic acid thereto; High acid value unsaturated polyester obtained by adding an epoxy group-containing unsaturated monomer to high acid value polyester; maleated polybutadiene, styrene-maleic acid co-polymer A hydroxyl group-containing unsaturated monomer is added to an acid anhydride-containing polymer such as a polymer. Unsaturated resins and the like.

As the resin containing no photosensitive functional group, for example, a high acid value acrylic resin obtained by polymerizing a polymerizable monomer containing (meth) acrylic acid; and a basic monomer such as dimethylaminoethyl (meth) acrylate. Examples thereof include amino group-containing acrylic resin obtained by polymerizing a polymerizable monomer containing; high acid value polyester; maleated polybutadiene; hydrolyzate or half-esterified product of styrene-maleic anhydride copolymer.

Examples of the self-water-soluble polymer include those obtained by partially esterifying and onium chloride of the epoxy group of the epoxy group-containing resin, or by onium chloride of the epoxy group. By using a saturated acid and / or a polymerizable unsaturated acid as a counter ion of an acid and / or onium chloride for esterification, it is possible to obtain a resin with or without a photosensitive functional group. it can.

Examples of the additive having a crosslinkable and curable photosensitive functional group which is a component other than the resin which can be contained in the resin composition for forming the photosensitive coating layer of the cover-coated resist of the present invention include: (Meth) acrylates of polyols; (meth) acrylates of oligomers such as polyethers, polyesters and polyurethanes; low molecular weight oligomers having two or more epoxy groups in one molecule.

The mixing ratio of the resin and these oligomers is not strictly limited, but generally, the resin / oligomer weight ratio is 100/0 to 40/60, preferably 100 /.
The range of 0 to 60/40 is preferable.

The photopolymerization initiator that can be contained in the photocurable resin composition for forming the photosensitive coating layer of the cover-coated resist of the present invention to carry out the crosslinking and curing by light irradiation is a polymerization with an actinic ray. Photopolymerization initiator alone to start,
A combination of a photopolymerization initiator and a sensitizer, or a photopolymerization initiator system in which a radical generator and a sensitizer are combined can be used.

That is, a substance which is decomposed by itself by photoexcitation or by an interaction with a sensitizer, more specifically, by a cleavage reaction of itself or a hydrogen abstraction reaction from another molecule, crosslinking of the photosensitive functional group. A compound or the like which generates an active group for a reaction or a polymerization reaction can be used as a photopolymerization initiator.

Further, specific examples of the photopolymerization initiator that can be contained in the photocurable resin composition forming the photosensitive coating layer of the cover-coated resist of the present invention include the following. These can be appropriately selected and used according to the characteristics of actinic rays.

Aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzyl, xanthone, thioxanthone and anthraquinone; acetophenone, propiophenone,
α-hydroxyisobutylphenone, α, α′-dichloro-4-phenoxyacetophenone, 1-hydroxy-
Acetophenones such as 1-cyclohexylacetophenone and acetophenone; benzoyl peroxide, tert
-Butyl-peroxybenzoate, tert-butyl-peroxy-2-ethylhexanoate, tert-butyl hydroperoxide, di-tert-butyldiperoxyisophthalate, 3,3 ', 4,4'-tetra ( tert-Butylperoxycarbonyl) organic peroxides such as benzophenone; diphenylhalonium salts such as diphenyliodonium bromide and diphenyliodonium chloride; organic halides such as carbon tetrachloride, carbon tetrabromide, chloroform and iodoform; 3-phenyl -5-isoxazolone, 2,4,6-tris (trichloromethyl)-
Heterocyclic and polycyclic compounds such as 1,3,5-triazinebenzanthrone; 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1, Azo compounds such as 1'-azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis (2-methylbutyronitrile); iron-allene complex (Iron-
Arene Complex: European Patent No. 152377); titanocene compound (JP-A-63-22111)
No. 0); etc.

Suitable examples of the above-mentioned iron-allene complex include, for example, the following general formulas (I), (II) and (III).
Can be mentioned.

[0041]

[Chemical 1]

In the above formula, X represents BF ₄ , PF ₆ , AsF ₆ or SbF ₆ ; R ₁ and R ₂ are each 1 to 1 carbon atoms.
A linear or branched alkyl group of 6, for example, a methyl group,
It represents an ethyl group, an isopropyl group, an n-butyl group or the like.

Further, preferred examples of the titanocene compound include those represented by the following general formula (IV).

[0044]

[Chemical 2] In the formula, two R _3's each independently represent a cyclopentadienyl group which is unsubstituted or substituted with 1 to 2 methyl groups (preferably cyclopentadienyl or methylcyclopentadienyl); R ₄ and R ₅ are each independently the following formula

[0045]

[Chemical 3]

[Wherein R ₆ is a fluorine atom, --CF ₃ or --C
Represents F ₂ CH ₃ , and R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, a fluorine atom, —CF ₃ , —CF ₂ CH ₃ , C ₁
To C ₁₈ alkyl group, alkoxy group or

[0047]

[Chemical 4]

Is shown].

Specific examples of the titanocene compound include:
For example

[0050]

[Chemical 5]

[0051]

[Chemical 6]

And the like.

The amount of these polymerization initiators used is not critical and can be varied within a wide range depending on the type of the initiator. Generally, the above-mentioned photocurable resin solid content 10 is used.
0.1 to 25 parts by weight, preferably 0.2 to 0 parts by weight
It can be in the range of 10 parts by weight. If it is used in a large amount exceeding 25 parts by weight, the stability of the obtained composition tends to be lowered.

In the photocurable resin composition for forming the photosensitive coating layer of the cover-coated resist of the present invention, the photosensitivity can be significantly improved by using a spectral sensitizer in combination with the photopolymerization initiator. . Specific examples of such spectral sensitizers include thioxanthene-based, xanthene-based,
Examples thereof include ketones, thiopyrylium salt-based, base styryl-based, merocyanine-based, 3-substituted coumarin-based, cyanine-based, acridine-based, and thiazine-based dyes.

The amount of these spectral sensitizers to be used varies depending on the type, the photocurable resin (including a mixture thereof with a polyvinyl monomer, etc.) and / or the type of the photopolymerization initiator, and is strictly specified. It is difficult to do so, but generally speaking, it is 0.1 to 1 per 100 parts by weight of the photocurable resin solid content.
Amounts of 0 parts by weight, preferably 0.3 to 5 parts by weight are suitable. If the amount of the spectral sensitizer used is less than 0.1 part by weight, the photosensitivity of the coating film is lowered, which is not preferable, and if it is more than 10 parts by weight, the spectral sensitizer is uniformly added to the composition. It tends to be difficult to maintain the condition.

Specific examples of the spectral sensitizer that can be used in combination with the photopolymerization initiator in the photocurable resin composition for forming the photosensitive coating layer of the cover-coated resist of the present invention are shown below. Is.

(1) Xanthene-based and thioxanthene-based dyes: the following formula

[0058]

[Chemical 7]

In the formula, A is an oxygen atom or a sulfur atom; X ₁ and X ₂ are each a hydrogen atom or a halogen atom such as chlorine and bromine; Y ₁ is a carbon atom or a nitrogen atom (provided that Y ₁ is When it is a carbon atom, it is a double bond between adjacent carbon atoms (indicated by a dotted line), and when Y ₁ is a nitrogen atom, it is a single bond between adjacent carbon atoms. Z is an oxygen atom (in this case, a double bond between adjacent carbon atoms), a lower alkoxy group or a lower alkanoyloxy group; R ₁₁ is a lower alkyl group, a hydroxy lower alkyl group, a lower A xanthene or thioxanthene dye represented by: R ₁₂ is an alkoxy lower alkyl group, a di lower alkylamino lower alkyl group or an aryl group; and R ₁₂ is a lower alkoxy group or a di lower alkylamino group. Examples thereof include those described in JP-A-62-31848.

(2) Ketone dye: the following formula

[0061]

[Chemical 8]

In the formula, R ₁₃ represents a lower alkyl group such as methyl or ethyl; R ₁₄ represents a hydrogen atom or —CO—C ₆ H ₅ ;

(3) (Thio) pyrylium salt dye: the following formula

[0064]

[Chemical 9]

In the formula, R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an ethylenyl group, a styryl group, an alkoxy group, a phenyl group,
Naphthyl group, alkylphenyl group, alkoxyphenyl group, a hydroxyphenyl group, a halophenyl group, a nitrophenyl group, an aminophenyl group, a nitro group, an amino group or a hydroxyl group; X ₃ represents an oxygen atom or a sulfur atom; Y ₂ ^- Represents an anion functional group, and a pyrylium salt or a thiopyrylium salt represented by can be mentioned. Here, examples of the anionic functional group represented by Y ₂ include perchlorate, fluoroborate, chloroaluminate, chloroferrate, sulfaacetate, methosulfate, fluoroantimonate, thiocyanate and the like (for example, JP-A-61). -21383
No. 8).

(4) Base styryl dye: the following formula

[0067]

[Chemical 10]

In the formula, X ₄ represents a group having a heterocycle shown below,

[0069]

[Chemical 11]

The base styryl dyes represented by:

(5) Merocyanine dye: the following formula (A)

[0072]

[Chemical 12]

In the formula, R ₁₈ and R ₁₉ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; n represents an integer of 1 to 3; X ₅ represents a group shown below,

[0074]

[Chemical 13]

The following formula (B)

[0076]

[Chemical 14]

In the formula, each of X ₆ and X ₇ represents a sulfur atom, an oxygen atom or —C (CH ₃ ) ₂ —; R ₂₀ , R ₂₁ and R ₂₂ are each a hydrogen atom and have 1 to 6 carbon atoms. The following formula (C) represents an alkyl group or an aryl group.

[0078]

[Chemical 15]

In the formula, R ₂₀ , R ₂₁ and R ₂₂ each represent a hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms; and X ₈ represents a hydrogen atom or an alkali metal. Examples thereof include dyes (see, for example, JP-A-61-213838).

(6) 3-Substituted coumarins: 3-substituted coumarins represented by the following structural formulas can be mentioned (see JP-A-61-97650).

[0081]

[Chemical 16]

[0082]

[Chemical 17]

[0083]

[Chemical 18]

[0084]

[Chemical 19]

[0085]

[Chemical 20]

[0086]

[Chemical 21]

[0087]

[Chemical formula 22]

(7) 3,4-Substituted Coumarins: The following formula (D)

[0089]

[Chemical formula 23]

In the formula, R ₂₃ and R ₂₄ are the same or different and each represents a lower alkyl group such as methyl, ethyl, propyl, isopropyl and butyl; R ₂₅ is a hydrogen atom or methyl, ethyl, propyl, isopropyl, Lower alkyl groups such as butyl, methoxymethyl, methoxyethyl,
Alkoxyalkyl groups such as ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, etc., Hydroxyalkoxyalkyl groups such as hydroxymethoxyethyl, hydroxyethoxyethyl, hydroxyproxyethyl, hydroxymethoxypropyl, hydroxyethoxypropyl, hydroxypropoxypropyl, etc. Represents a alkoxycarbonylalkyl group such as methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylpropyl, butoxycarbonylbutyl and the like.

Specific examples of the sensitizer include 3,4-substituted coumarins represented by the following structural formula (see Japanese Patent Application No. 3-223759).

[0092]

[Chemical formula 24]

[0093]

[Chemical 25]

(8) Cyanine dye: the following formula (E)

[0095]

[Chemical formula 26]

In the formula, R ₂₆ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group or a dialkylamino group; R ₂₇ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group. X ₉ represents a halogen atom; n represents an integer from 1 to ₃ ; Y ₃ represents a group shown below,

[0097]

[Chemical 27]

The following formula (F)

[0099]

[Chemical 28]

In the formula, R ₂₈ and R ₂₉ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group; X ₁₀ represents a halogen atom; The group having a ring represents the group shown below,

[0101]

[Chemical 29]

The following formula (G)

[0103]

[Chemical 30]

In the formula, R ₃₀ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an alkoxy group; R ₃₁
Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group; X ₁₁ represents a halogen atom;
Represents an integer up to; Y ₄ represents a group shown below,

[0105]

[Chemical 31]

Examples thereof include cyanine dyes represented by (JP-A-61-213838).

If necessary, the photocurable composition for forming the photosensitive coating layer of the film resist of the present invention may contain a nitrogen-containing compound represented by the following general formulas (a) to (f). it can.

[0108]

[Chemical 32]

In the formula, X represents a hydrogen atom or a hydroxyl group;
R ₃₂ , R ₃₃ and R ₃₄ each represent a hydrogen atom, a chlorine atom or an alkyl group having 1 to 6 carbon atoms,

[0110]

[Chemical 33]

In the formula, R ₃₅ and R ₃₆ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

[0112]

[Chemical 34]

In the formula, R ₃₇ , R ₃₈ and R ₃₉ each represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 12 carbon atoms,

[0114]

[Chemical 35]

In the formula, R ₄₀ , R ₄₁ and R ₄₂ each represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms,

[0116]

[Chemical 36]

In the formula, R ₄₃ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms,

[0118]

[Chemical 37]

In the formula, R ₄₄ and R ₄₅ each represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 3.

Examples of the compound represented by the general formula (a) include benzotriazoles such as benzotriazole, methylbenzotriazole, N-hydroxybenzotriazole, chlorobenzotriazole, dichlorobenzotriazole and trichlorobenzotriazole. be able to.

As the compound represented by the general formula (b),
Examples thereof include pyrazoles such as 3-methylpyrazole and 3,5-dimethylpyrazole.

As the compound represented by the general formula (c),
For example, a compound represented by the following formula and the like can be mentioned.

[0123]

[Chemical 38]

As the compound represented by the general formula (d),
For example, a compound represented by the following formula and the like can be mentioned.

[0125]

[Chemical Formula 39]

As the compound represented by the general formula (e),
For example, a compound represented by the following formula and the like can be mentioned.

[0127]

[Chemical 40]

Examples of the compound represented by the general formula (f) include compounds represented by the following formulas.

[0129]

[Chemical 41]

Among the above-mentioned nitrogen-containing compounds, particularly preferable are the benzotriazoles represented by the general formula (a).

The nitrogen-containing compound may be used alone or in combination of two or more in the photocurable resin composition for forming the photosensitive coating layer of the cover-coated resist of the present invention. In general, 0.01 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the curable resin solid content.
It can be in the range of 1 to 10 parts by weight.

When the above-mentioned nitrogen-containing compound is blended in the photocurable resin composition, the sensitizing action is amplified and the sensitivity becomes very high, and at the same time, the resolution of the image is also amplified.

Further, in the non-photosensitive coating layer and / or the resin composition for forming the photosensitive coating layer, non-reaction of dyes, color pigments, adhesion improvers, polymerization inhibitors, coating surface improvers, plasticizers, etc. Property additive or a solvent such as water or an organic solvent for facilitating coating can be included.

In the cover coat transfer film and the resist with a cover coat of the present invention, it is important that the adhesive force between the layers is sufficiently controlled, and the adhesive strength between the layers (1 according to JIS Z 0287-1980).
80 ° peel strength) is generally 1.5-10 g / c between the support film / non-photosensitive layer of the cover coat transfer film.
m, preferably 1.5 to 5 g / cm; the non-photosensitive layer / photosensitive layer of the resist with a cover coat can be usually 20 g / cm or more.

The adjustment of the adhesive force between each of these layers can be easily carried out by selecting the material of each layer, selecting the reactive and non-reactive additives, and the like.

The cover-coated resist of the present invention can be prepared, for example, as follows.

(A) A non-photosensitive coating layer is applied on a support film and dried.

(B) A sticky photosensitive coating layer is applied on a substrate at room temperature and dried.

(C) After the non-photosensitive coating layer is adhered onto the adhesive photosensitive coating layer, the supporting film is peeled off, the non-photosensitive coating layer is transferred onto the photosensitive coating layer, and a cover coat is carried out.

Next, a pattern forming method using the above-described resist with a cover coat of the present invention will be described.

According to the present invention, the resist with a cover coat formed on the substrate on which the pattern is to be formed is selectively exposed, and then developed to remove the unexposed portion. A method of forming is provided.

According to the present invention, a resist with a cover coat formed on a base material made of a material which can be etched on at least one side is selectively exposed and then developed to etch the exposed portion. And a resist film remaining on the obtained pattern is peeled off, to provide an etching pattern forming method.

Exposure of the cover-coated resist of the present invention,
The development is performed, for example, by first forming the cover-coated resist of the present invention by the method described above, and then exposing the actinic ray through the non-photosensitive coating layer in a patternwise manner so that the pattern to be formed is drawn, It can be carried out by developing the non-photosensitive coating layer and the unexposed areas of the photosensitive coating layer with a developing solution that selectively dissolves.

For patternwise exposure, a method known per se such as a contact method using a photomask, a projection method and a direct writing method can be used.

As a light source for exposure, ultra high pressure, high pressure or low pressure mercury lamps that generate light including ultraviolet rays, chemical lamps, metal halide lamps, ultraviolet lasers, sunlight, lamps that generate visible light, and visible light lasers. And the like can be used depending on the photosensitive characteristics of the photosensitive layer.

As the substrate, for example, a metal or an inorganic or organic substrate or a film on which a metal foil is laminated or a metal is plated or vapor-deposited can be used. Further, the developing solution that can be used for development varies depending on the type of the photosensitive coating layer. For example, when the resin in the photosensitive resin composition forming the photosensitive coating layer contains an anionic group such as a carbonyl group, A weak alkaline aqueous solution,
When a cationic group such as an amino group is included, a weak acid aqueous solution can be used. Examples of the weak alkaline aqueous solution include dilute aqueous solutions of caustic soda, sodium carbonate, ammonia and the like, and examples of the weak acid aqueous solutions include dilute aqueous solutions of formic acid, acetic acid, lactic acid and the like. Further, in the case of a self-water-soluble resin containing an onium base or the like, water can be used as the developing solution.

The pattern thus formed is, for example, a printing plate such as a flat plate or a relief printing plate, an offset printing plate, or a PS plate.
It can be used for producing plates, reliefs, displays, resists other than etching, printed circuit boards, and the like.

In the case of the etching pattern forming method, the developed substrate is used as an etching solution capable of etching the metal on the surface of the substrate (for example, an aqueous solution of ferric chloride, cupric chloride, etc.).
The metal part exposed by the above development can be removed by etching. Then, the remaining resist film on the metal is stripped with a stripping agent (for example, acid, alkaline aqueous solution, solvent, etc.) to obtain an etching pattern.

If the substrate is a metal, or an inorganic or organic substrate or a film on which a metal foil is laminated or a metal is plated or vapor-deposited, and etching processing is required, it is developed as described above. It is also possible to obtain an etching pattern by plating the exposed metal surface with solder or the like, peeling the resist film with a peeling agent, and then removing the exposed metal with an etching solution that selectively etches.

According to the cover coat mounting method of the present invention described above, it is possible to obtain a resist with a cover coat having high resolution, high sensitivity, high reliability, and high workability without deterioration of photosensitivity due to oxygen. Therefore, it has excellent fine image pattern forming ability and can be effectively used in fields such as printed circuit boards and metal fine processing.

[0151]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, "parts" and "%" all indicate "parts by weight" and "% by weight" unless otherwise specified.

Production Example 1 Methyl methacrylate 10 parts, ethyl acrylate 35
Parts, 55 parts of acrylic acid, azobisisobutyronitrile 2
11 parts of a monomer mixture liquid under a nitrogen gas atmosphere.
It was added dropwise to 90 parts of isobutyl alcohol kept at 0 ° C. over 3 hours. After dropping, after keeping at 110 ° C for 1 hour,
A mixed solution containing 1 part of azobisdimethylvaleronitrile and 10 parts of isobutyl alcohol was added dropwise over 1 hour, and the mixture was kept for 5 hours to obtain a high acid value acrylic resin.
Next, 80 parts of glycidyl methacrylate is added to this solution,
Add 0.1 parts of hydroquinone and 0.8 parts of tetraethylammonium bromide, and add 11 while blowing air.
The reaction was carried out at 0 ° C for 5 hours, and the photocurable resin solution 1 (acid value 1.
1 mol COOH / kg resin, degree of unsaturation 3.13 mol / k
g resin, resin Tg-2 ° C., solid content 64%) were obtained.

Production Example 2 0-Novolak cresol type epoxy resin 1000 parts (molecular weight about 500, epoxy equivalent 198) acrylic acid 363 parts N-methyldiethanolamine 119 parts 2-methoxypropanol 1000 parts A mixed solution consisting of 1000 parts at 60 ° C. for 7 hours. The reaction was carried out to obtain a photocurable resin solution 2 (0.67 mol / kg resin of quaternary ammonium salt group, 3.4 mol / kg resin of unsaturation degree, resin Tg 5 ° C., solid content 60%).

Production Example 3 Glycidyl methacrylate 57 parts N, N'-dimethylaminoethyl methacrylate 20 parts Methyl methacrylate 5 parts n-Butyl acrylate 18 parts Azobisisobutyronitrile 2.5 parts A monomer mixture liquid An acrylic resin solution was obtained in the same manner as in Production Example 1 except that the above was used. next,
29 parts of acrylic acid, 0.1 part of hydroquinone,
Add 1.0 parts of tetramethylammonium bromide,
The reaction was carried out at 100 ° C. for 5 hours while blowing air, and the photocurable resin solution 3 (tertiary amino group: 0.99 mol / kg resin, degree of unsaturation 3.1 mol / kg resin, resin Tg 0 ° C., solid content 56 %) Was obtained.

Preparation Example 4 Methyl methacrylate 45 parts Acrylic acid 55 parts Azobisisovaleronitrile 1.5 parts The same procedure as in Preparation Example 1 except that a mixture consisting of 1.5 parts was used as a monomer mixture, and the photocurable resin 4 (acid Value 1.1
Mol COOH / kg resin, degree of unsaturation 3.13 mol / kg
Resin, resin Tg 23 ° C., solid content 64%) was obtained.

Example 1 A resin solid content of 10 was added to the photocurable resin solution 1 obtained in Production Example 1.
Photopolymerization initiator (benzoin ethyl ether) for 0 part
5 parts were added to prepare Photosensitive Composition 1. This photosensitive composition 1 was applied on a tin plate to a dry film thickness of 20 μm and dried at 80 ° C. for 10 minutes, and the glass transition temperature was measured. The results are shown in Table-1.

Polyvinyl alcohol (polymerization degree: 170) was formed on a polyethylene terephthalate film having a thickness of 75 μm.
0, Tg 65 ° C, oxygen transmission rate 2 × 10 ^-14 cc · cm /
A 12% aqueous solution (cm ² · sec · cmHg) was uniformly applied to a dry film thickness of 2 μm and dried at 80 ° C. for 10 minutes to obtain a cover coat transfer film. Separately, the photosensitive composition 1 was applied onto a glass epoxy substrate laminated with a 35 μm copper foil so that the dry film thickness was 15 μm,
A photosensitive coating layer is formed by drying at 80 ° C. for 10 minutes, the non-photosensitive coating layer of the cover coat transfer film is adhered onto the photosensitive coating layer, and then the polyethylene terephthalate film is peeled off to form a resist with a cover coat. It was created. The adhesive strength between the layers is shown in Table-2.

Examples 2 to 4 To form the non-photosensitive coating layer, 50 parts of polyvinyl alcohol having a degree of polymerization of 1700, 25 parts of polyvinyl alcohol having a degree of polymerization of 500, polyvinyl acetate emulsion (solid content 40
%) 62.5 parts of an aqueous resin solution prepared by dissolving 800 parts of deionized water (Tg of resin: 45 ° C., oxygen permeability: 7 × 10 ⁻¹³ cc
^{· Cm / cm 2 · sec ·} cmHg) with a photosensitive composition of the formulation shown in Table 1 in the formation of photosensitive film layer 2
Resists 2 to 4 with cover coat were obtained in exactly the same manner as in Example 1 except that 4 was used. The glass transition temperatures of the photosensitive compositions 2 to 4 are shown in Table 1 and the resists 2 to 4 with a cover coat.
The interlayer adhesive strength of is shown in Table-2.

Comparative Example 1 A 75 μm polyethylene terephthalate film was directly coated with Photosensitive Composition 1 in the same manner as in Example 1 to obtain a film resist 5. The interlayer adhesive strength of the film resist 5 is shown in Table-2. Then, the photosensitive film layer of the obtained film resist was brought into close contact with a glass epoxy substrate laminated with the same copper foil as in Example 1 to obtain a substrate with a film resist.

Comparative Example 2 For the formation of the non-photosensitive coating layer, an aqueous resin solution (Tg of resin was prepared by dissolving 75 parts of methyl cellulose and 62.5 parts of polyvinyl acetate emulsion (solid content 40%) in 800 parts of deionized water.
43 ° C, oxygen transmission rate 8.4 × 10 ^-11 cc · cm / cm ²
-Sec. CmHg) was used, and a resist 6 with a cover coat was obtained in exactly the same manner as in Example 4.

The interlayer adhesive strength of the cover-coated resist 6 is shown in Table 2.

[0162]

[Table 1]

The abbreviations or structures in Table 1 have the following meanings.

(Note 1) Titanocene compound (T-1)

[0165]

[Chemical 42]

(Note 2) Spectral sensitizer (A-1)

[0167]

[Chemical 43]

[0168]

[Table 2]

Application Examples 1 to 7 Thus, the cover coat resists 1 to 3 and the film resist 5 obtained in Examples 1 to 3 and Comparative Example 1 were exposed with an ultrahigh pressure mercury lamp through a test pattern mask. The test pattern is line (μm) / space (μm) = 2
00/200, 150/150, 100/100, 80
/ 80, 60/60, 40/40, 30/30 were used. Then, the film is developed with a predetermined developing solution and conditions (the film resist 5 peels off the supporting film before development), etched with ferric chloride, and the circuit pattern formed by peeling off the resist with a predetermined peeling solution is observed. did. The results are shown in Table-3.

With respect to the resists 4 and 6 with cover coat obtained in Example 4 and Comparative Example 2, the same pattern as the above test pattern mask was exposed by an direct writing method with an argon ion laser having a wavelength of 488 nm. Next, development was performed with a predetermined developing solution and conditions, after etching with ferric chloride, the resist was peeled off with a predetermined peeling solution, and the state of the circuit pattern formed was observed. The results are shown in Table-3.

[0171]

[Table 3]

Claims (5)

[Claims] 1. A support film and a film formed thereon,
The non-photosensitive coating surface of a transfer film having a non-photosensitive coating layer, which has substantially no tackiness at room temperature, oxygen barrier property and is soluble in a developing solution, is coated with a photosensitive coating film having tackiness at room temperature. A method for attaching a cover coat, which comprises bringing the substrate having a layer into close contact with the photosensitive film layer, peeling the supporting film, and transferring the non-photosensitive film layer to the photosensitive film layer to form a cover coat. . 2. The non-photosensitive coating layer of the transfer film has a thickness of 0.5 to 5 μm and an oxygen permeability of 5 × 10 ⁻¹² cc ·
The method for mounting a cover coat according to claim 1, wherein the method is not more than cm / cm ² · sec · cmHg. 3. The cover coat according to claim 1, wherein the glass transition point of the non-photosensitive coating layer of the transfer film is 20 ° C. or higher and the glass transition point of the photosensitive coating layer on the substrate is 5 ° C. or lower. Wearing method. 4. The photosensitive coating layer of a substrate coated with a cover coat according to claim 1 is selectively exposed to obtain a desired pattern and then developed to remove unexposed portions. A pattern forming method characterized by the above. 5. A support film and a support film formed thereon,
A material capable of etching at least one side of the non-photosensitive coating surface of a transfer film having a non-photosensitive coating layer which has substantially no tackiness at room temperature, oxygen barrier property, and is soluble in a developer. Of the substrate having a photosensitive coating layer having a tacky photosensitive coating layer at room temperature on its etchable surface, the supporting film is peeled off, and the non-photosensitive coating layer is replaced with the photosensitive coating layer. After transferring to a cover coat,
The photosensitive coating layer is selectively exposed to obtain a desired pattern, and then developed to remove the unexposed portion, and the exposed portion of the etchable surface of the substrate is removed by etching. The method for forming an etching pattern, characterized in that the remaining resist film is peeled off.