JPH0553319A - Film resist for direct plotting and etching method using this film resist - Google Patents

Abstract

PURPOSE:To obtain the film resist which has a high resolution, obviates the degradation in photosensitivity by oxygen and has the excellent ability to form fine image patterns by a direct plotting method and the etching method using this film resist. CONSTITUTION:This film resist for direct plotting is constituted by forming a nonphotosensitive coating layer which is soluble in a developer, has an oxygen barrier property, is substantially nontacky at ordinary temp. and has 1 to 5mum film thickness on a base film and further forming a photosensitive coating layer which is tacky at ordinary temp. on the nonphotosensitive coating layer. This etching method consists in using this film resist.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film resist for direct writing, and more specifically, it forms an oxygen-blocking non-adhesive non-photosensitive coating layer on a support film, and further has a tackiness on the upper layer. The present invention relates to a film resist for direct writing, on which a photosensitive film layer is formed, capable of forming a fine pattern, and an etching method using the film resist.

[0002]

2. Description of the Related Art In recent years, CAD (Co) has been developed in order to cope with stricter alignment (accuracy) accuracy accompanying the shortening of the time for producing a prototype circuit for electronic equipment and the multilayering of circuit boards.
mputer Aided Design) and the actinic ray irradiation device are directly connected, and the pattern formation by the direct writing method is drawing attention.

On the other hand, in the conventional photolithography method in which exposure is performed through a photomask, a photomask is created from CAD data for each circuit. Not suitable.

In addition, the requirement for alignment accuracy has become extremely strict with the increase in the number of circuit boards. However, in the photomask method, the photomask itself expands and contracts due to changes in the environment (temperature, humidity), and thus the accuracy requirement. It has become difficult to meet.

Therefore, a direct drawing method using a laser beam as an active energy light source has been attracting attention as a method for solving these problems.

Resists used in the direct drawing method are roughly classified into dry film resists and liquid resists.

Dry film resists usually consist of a tacky photosensitive resin layer on a light-transmissive support film and its protective film.

An image forming method by a direct drawing method using a dry film is a dry film comprising a light-transmissive support film, a photosensitive resin layer and a protective film.
After peeling off the protective film, press the photosensitive resin layer onto the substrate, irradiate the active light that blinks according to the CAD data through the light transmissive support film, and then selectively dissolve the unexposed area. The development process is performed with the developing solution to form a desired pattern on the substrate.

Further, when the substrate is a material such as a copper clad laminate capable of being etched, it is further subjected to an etching treatment, or after an image is formed and a metal such as copper exposed is plated with metal. Etching patterns can be formed by removing the cured resist on the substrate with an alkaline aqueous solution or the like, and then treating the exposed portions with an etching liquid that selectively etches the exposed portions.

However, in recent years, the density of electronic circuits has been further increased, and a high resolution has been required to form a circuit pattern, and the dry film resist cannot meet the demand.

That is, since the dry film resist is exposed through the light-transmissive support film, it is preferable that the support film be as thin as possible in order to obtain high resolution, but the photosensitive resin layer is applied. To function as a support for a certain thickness, typically 1
A thickness of 5 to 50 μm is required, which makes it difficult to obtain high resolution.

If the support film can be peeled off and exposed to light, the resolution can be greatly improved, but in this case, due to the tackiness of the photosensitive layer, dust and dirt in the environment tend to adhere, and the working environment must be markedly clean. It is difficult to put it into practical use because of the problems that it must be obtained and that the photosensitivity layer comes into contact with oxygen in the atmosphere, resulting in a significant decrease in photosensitivity.

On the other hand, if a liquid resist is used, the problem of resolution is solved, and after forming a photosensitive liquid resist film on the substrate, a cover coat film having an oxygen blocking property is further formed thereon. As a result, the problem of decreased photosensitivity due to oxygen can be solved.

However, in the case of a liquid resist, application of the liquid resist, drying, application of a cover coat,
Since a series of operations such as drying and the like are required, the whole manufacturing process becomes complicated, and there are drawbacks such as defects due to dust, dust, etc. in the coating and drying processes, and the like. There is a fundamental problem that some substrates cannot be processed.

[0015]

DISCLOSURE OF THE INVENTION As a result of earnest studies on a direct writing resist which does not have the above problems, the present inventors have found that the problems of the dry film resist and the liquid resist described above can be solved simultaneously. The present invention has been completed by discovering such a film resist.

Thus, according to the present invention, a non-photosensitive coating layer having a thickness of 1 to 5 μm, which is formed on a supporting film, is soluble in a developing solution, has an oxygen barrier property, and is not tacky at room temperature. And a film resist for direct writing, comprising a photosensitive coating layer which is provided on the non-photosensitive coating layer and has an adhesive property at room temperature.

According to the present invention, there is also provided a film resist for direct writing, in which a protective film is further laminated on the photosensitive film layer if necessary.

According to the present invention, there is further provided an etching method by a direct drawing method using the above film resist.

The film resist of the present invention has a high resolution,
Since there is no decrease in photosensitivity due to oxygen and it can be applied to a through-hole substrate, by using the film resist of the present invention, a high-density circuit substrate can be efficiently manufactured,
Further, as described above, the complicated work such as resist coating and drying at the manufacturing site is not required, so that the circuit board having excellent workability can be manufactured.

According to the etching method using the film resist of the present invention, first, the adhesive photosensitive coating layer of the resist film is pressure-bonded onto a substrate such as a copper-clad laminate, and then the support film is peeled off to directly After exposure by the drawing method, a circuit pattern or the like can be obtained by developing and etching as in the case of the conventional dry film. The support film of the resist of the present invention has a heat resistance necessary for applying a non-photosensitive layer and a photosensitive layer and drying to obtain a uniform film.
There is no particular limitation as long as it has solvent resistance, and it may be transparent or opaque, for example, polyester film, nylon film, vinylidene chloride film, vinyl chloride film, polyethylene, synthetic resin film such as polypropylene, or A film obtained by further subjecting them to an activation treatment such as corona treatment, a metal foil such as an aluminum foil, or the like can be used.

The non-photosensitive coating layer of the resist of the present invention has a thickness of 1
It is ˜5 μm, is substantially non-adhesive, and has an oxygen blocking ability. Since the non-photosensitive coating layer needs to be substantially tack-free, its glass transition point is 20 ° C.
As described above, more preferably 30 ° C. or higher.

The oxygen barrier property of the non-photosensitive coating layer is such that the oxygen gas permeability of the film is 5 × 10 ⁻¹² cc · cm / cm ² · se.
It is preferably c · cmHg or less. Oxygen gas permeability here is ASTM standards D-1434-82.
It is a value measured according to the method described in (1986).

The non-photosensitive coating layer must not be photosensitive. That is, if it is photosensitive, it hardens during exposure and it takes a long time to peel off the resist film after etching, which is not preferable in terms of work.

Further, the non-photosensitive coating layer needs to be completely dissolved in the developing solution. If it is not soluble in the developing solution, the non-photosensitive coating layer must be peeled off before development, which is disadvantageous in terms of productivity.

As the film-forming resin for forming the non-photosensitive film layer satisfying such conditions, polyvinyl alcohol, partially saponified polyvinyl acetate or a mixture thereof, or a mixture of polyvinyl alcohol and a vinyl acetate polymer is used. Etc., these are excellent in film forming property,
It is preferable because it has good solubility in an aqueous developer such as water, diluted alkaline water, or diluted acid water.

On the other hand, the photosensitive coating layer of the resist of the present invention needs to be tacky, and its glass transition point is 5 ° C.
The following is preferable. Further, since the photosensitive coating layer needs to be crosslinked and cured by irradiation with actinic rays, the resin and / or additives in the photosensitive resin composition forming the photosensitive coating layer may be directly or indirectly irradiated with light. It must contain a photosensitive functional group that is activated and reacts to crosslink and cure.

When the photosensitive functional group in the composition is indirectly activated by light, an initiator or an initiator / sensitizer (initiator) which is activated by light and causes a reaction of the functional group is generated. System) is required. In the direct writing method, an argon ion laser mainly having a wavelength of 488 nm is often used as an active light source, so that it is particularly preferable to use an initiator system which is activated by light having a wavelength of 488 nm.

Further, the unexposed portion of the composition must be soluble in the developing solution. The developer is preferably water, a weakly alkaline or weakly acidic aqueous developer, but in order to be developable with such an aqueous developer, the composition has a carboxyl group which forms a salt which can be dissociated by neutralization, A functional group such as an amino group is used in an amount of about 0.5 to 3.0 mol per 1 kg of the resin,
Alternatively, a functional group such as a water-soluble quaternary ammonium base or tertiary sulfonium base (onium base) may be added to the resin 1k.
It is preferable to contain about 0.3 to 2.0 mol per g.

Examples of the film forming component of the composition include a resin component and a low molecular weight compound having a crosslinkable and curable photosensitive functional group such as a polyvinyl monomer and a low molecular weight epoxy oligomer which are optionally added.

The resin component may or may not contain a cross-linking curable functional group itself, but the cross-linking curable photosensitive functional group as a whole film-forming component forms a film-forming component 1.
Generally 1.0 to 7.0 mol per kg, preferably 2.0.
It is important to include in the range of mol to 5.0 mol. When the amount of the photosensitive functional group is less than 1.0 mol, the curability is deteriorated and it takes a long time to draw a pattern, and when it is more than 7.0 mol, the cured resist tends to be difficult to peel off.

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 and chalcone. Group, bisazide group, epoxy group, etc., among which can be relatively easily introduced into a resin or a low molecular weight compound (meth)
The acryloyl group is particularly preferred.

As the resin component, resins such as acrylic resin type, epoxy ester type, polyester resin type, maleated polybutadiene type and styrene-maleic anhydride copolymer 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, and 3,4-epoxycyclohexyl. High acid value unsaturated acrylic resin to which a (meth) acrylic acid ester of methanol is added; containing an epoxy group obtained by copolymerizing dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate and another 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 Add a hydroxyl group-containing unsaturated monomer to an acid anhydride-containing polymer such as a polymer And unsaturated resins.

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.

As the self-water-soluble polymer, for example, a polymer obtained by partially esterifying the epoxy group of an epoxy group-containing resin and onium chloride, or a polymer obtained by onium chloride of all of the epoxy group is included. By using a saturated acid and / or a polymerizable unsaturated acid as a counter ion for esterification and / or onium chloride, it is possible to obtain a resin having or without a photosensitive functional group in the resin.

The additives other than the resin contained in the resin composition forming the photosensitive coating layer of the resist of the present invention and having a crosslinkable and curable photosensitive functional group include (meth) acrylates of polyols, polyethers, Examples thereof include oligomeric (meth) acrylates such as polyester and polyurethane, and low molecular weight oligomers having two or more epoxy groups in one molecule.

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

As the photopolymerization initiator which can be contained in the photocurable resin composition for forming the photosensitive coating layer of the resist of the present invention in order to carry out crosslinking curing by irradiation with light, a photopolymerization initiator alone or a photopolymerization initiator is used. It is possible to use a combination of a photosensitizer and a sensitizer, or a photopolymerization initiator system in which a radical generator and a sensitizer are combined.

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

In the case of pattern formation by the direct drawing method, in order to perform fine etching processing with high productivity, it is desirable to increase the sensitivity of the resist photosensitive layer. For this purpose, it is necessary to select a photopolymerization initiator system having high sensitivity. Extremely important.

Specific examples of the photopolymerization initiator that can be contained in the photocurable resin composition forming the photosensitive coating layer of the resist of the present invention include the following.

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-A
rene Complex: See European Patent No. 152377); titanocene compounds (see JP-A-63-221110);

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

[0044]

[Chemical 1]

[0045]

[Chemical 2]

[0046]

[Chemical 3] In the above formula, X represents BF ₄ , PF ₆ , AsF ₆ or SbF ₆ ; R ₁ and R ₂ are each a linear or branched alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, It represents 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).

[0048]

[Chemical 4] In the formula, two R _3's are each independently unsubstituted or 1-2.
Represents cyclopentadienyl substituted with 4 methyl groups (preferably cyclopentadienyl or methylcyclopentadienyl); R ₄ and R ₅ are each independently of the formula

[0049]

[Chemical 5] [In the formula, R ₆ represents a fluorine atom, —CF ₃ or —CF ₂ CH ₃ , and R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a fluorine atom, —CF ₃ , —CF ₂ CH ₃ A hydrogen atom, a C ₁ -C ₁₈ alkyl group, an alkoxy group or

[0050]

[Chemical 6] Is shown].

Specific examples of the titanocene compound include:
For example

[0052]

[Chemical 7]

[0053]

[Chemical 8]

[0054]

[Chemical 9]

[0055]

[Chemical 10] And so on.

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 is 10
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.

When visible light is used as the active light source, among the above-mentioned polymerizable initiators, di-tert-butyldiperoxyisophthalate, 3,3 ', 4,4'-tetra (tert-butylperoxy) is particularly preferable. Carbonyl) benzophenone, iron-allene complexes and titanocene compounds are preferred compounds because they have high activity for crosslinking or polymerization.

In the photocurable resin composition for forming the photosensitive coating layer of the resist of the present invention, if a spectral sensitizer is used in combination with a photopolymerization initiator, the photosensitivity can be significantly improved. In particular, when using visible light as the active light source, 40
It is preferable to use a spectral sensitizer that is excited by light having a wavelength of 0 to 700 nm and has an interactive property with the above-mentioned photocurable resin or photopolymerization initiator. Specific examples thereof include thioxanthene type,
Examples thereof include xanthene-based, ketone-based, thiopyrylium salt-based, base styryl-based, merocyanine-based, 3-substituted coumarin-based, cyanine-based, acridine-based, and thiazine-based dyes. The "interaction" referred to here includes energy transfer and electron transfer from the excited spectral sensitizer to the photocurable resin or the photopolymerization initiator.

The amount of these spectral sensitizers to be used depends on the type and photocurable resin (or a mixture thereof with a polyvinyl monomer, etc., hereinafter referred to as “photocurable resin”) to be interacted with and / or light. Depending on the type of polymerization initiator, etc.,
Although it is difficult to specify exactly, generally speaking, the range of 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, is suitable per 100 parts by weight of the photocurable resin solid content. .. If the amount of the spectral sensitizer used is less than 0.1 parts 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 resist of the present invention are as follows. (1) Xanthene-based and thioxanthene-based dyes: the following formula

[0061]

[Chemical 11] In the formula, A is an oxygen atom or a sulfur atom; X ₁ and X ₂
Each is a hydrogen atom or a halogen atom such as chlorine or bromine; Y ₁ is a carbon atom or a nitrogen atom (however, when Y ₁ is a carbon atom, between adjacent carbon atoms (indicated by a dotted line)) Is a double bond, and when Y ₁ is a nitrogen atom, is a single bond with an adjacent carbon atom); and Z is an oxygen atom (in this case, is a double bond with an adjacent carbon atom). a bond), a lower alkoxy group or a lower alkanoyloxy group; R ₁₁ is a lower alkyl group, a hydroxy lower alkyl group, lower alkoxy-lower alkyl group, a di-lower alkylamino-lower alkyl group or an aryl group; R ₁₂ is Examples thereof include xanthene or thioxanthene dyes represented by a lower alkoxy group or a di-lower alkylamino group (for example, JP-A-62-3184). No. see Japanese).

(2) Ketone dye: the following formula

[0063]

[Chemical formula 12] 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) Thiopyrylium salt dye: the following formula

[0065]

[Chemical 13] 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,
Styryl group, alkoxy group, phenyl group, naphthyl group,
Alkylphenyl group, alkoxyphenyl phenylalanine group, hydroxyphenyl group, Harofueniru group, nitrophenyl group, aminophenyl group, a nitro group, an amino group or a hydroxyl group; X ₃ represents an oxygen atom or a sulfur atom; Y ₂ ^- is an anion Pyrylium salt or thiopyrylium salt represented by which represents a functional group can be mentioned. Examples of the anionic functional group represented by Y ₂ include perchlorate, fluoroborate, chloroaluminate, chlorophenolate, sulfaacetate, methosulfate, fluoroantimonate, thiocyanate and the like (for example, JP-A-61-213838). See the bulletin).

(4) Base styryl dye: the following formula

[0067]

[Chemical 14] In the formula, X ₄ represents a group having a heterocycle shown below,

[0068]

[Chemical 15] Examples thereof include base styryl dyes.

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

[0070]

[Chemical 16] In the formula, R ₁₈ and R ₁₉ are each a hydrogen atom or a carbon number of 1 to 4
Represents an alkyl group; and n represents an integer of 1 to 3; X
₅ represents a group shown below,

[0071]

[Chemical 17] Formula (B) below

[0072]

[Chemical 18] In the formula, X ₆ and X ₇ are each a sulfur atom, an oxygen atom or —C
(CH _{3) 2} - a represents; R _20, each represent a hydrogen atom R ₂₁ and R ₂₂ represents an alkyl group or an aryl group having up to 6 carbon atoms, following formula (C)

[0073]

[Chemical 19] In the formula, R ₂₀ , R ₂₁ and R ₂₂ are each a hydrogen atom or a carbon number of 1 to
Methocyanine dyes represented by up to 6 alkyl groups or aryl groups; X ₈ represents a hydrogen atom or an alkali metal (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).

[0075]

[Chemical 20]

[0076]

[Chemical 21]

[0077]

[Chemical formula 22]

[0078]

[Chemical formula 23]

[0079]

[Chemical formula 24]

[0080]

[Chemical 25]

[0081]

[Chemical formula 26]

[0082]

[Chemical 27]

[0083]

[Chemical 28]

[0084]

[Chemical 29]

[0085]

[Chemical 30]

[0086]

[Chemical 31]

[0087]

[Chemical 32]

[0088]

[Chemical 33]

[0089]

[Chemical 34]

[0090]

[Chemical 35]

[0091]

[Chemical 36]

[0092]

[Chemical 37]

[0093]

[Chemical 38]

[0094]

[Chemical Formula 39]

[0095]

[Chemical 40]

[0096]

[Chemical 41]

[0097]

[Chemical 42]

[0098]

[Chemical 43] (7) 3,4-substituted coumarins: the following formula (D)

[0099]

[Chemical 44] In the formula, R ₂₃ and R ₂₄ may be 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 and butyl. Lower alkyl groups such as methoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, and other alkoxyalkyl groups, hydroxymethoxyethyl, hydroxyethoxyethyl, hydroxyproxyethyl, hydroxymethoxypropyl, hydroxy Hydroxyalkoxyalkyl groups such as ethoxypropyl and hydroxypropoxypropyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylpropyl Represent alkoxycarbonylalkyl group such as butoxycarbonyl-butyl.

Specific examples of the sensitizer include 3,4-substituted coumarins represented by the following structural formula (Japanese Patent Application No. 2-321279).

[0101]

[Chemical 45]

[0102]

[Chemical 46]

[0103]

[Chemical 47]

[0104]

[Chemical 48]

[0105]

[Chemical 49]

[0106]

[Chemical 50] (8) Cyanine dye: the following formula (E)

[0107]

[Chemical 51] 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 of 1 to ₃ ; Y ₃ represents a group shown below,

[0108]

[Chemical 52] Formula (F)

[0109]

[Chemical 53] In the formula, R ₂₈ and R ₂₉ are each independently a hydrogen atom and a carbon number of 1 to
10 represents an alkyl group or an aryl group; X ₁₀ represents a halogen atom; and a group having a nitrogen-containing heterocycle represented by a dotted line in the formula represents a group shown below.

[0110]

[Chemical 54] The following formula (G)

[0111]

[Chemical 55] Wherein, R ₃₀ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an alkoxy group,; R ₃₁ is a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms; X ₁₁ is Represents a halogen atom; n represents an integer of 1 to 3; Y ₄ represents a group shown below;

[0112]

[Chemical 56] And cyanine dyes represented by the following formula (JP-A-61-213838).

In the photocurable composition for forming the photosensitive coating layer of the resist of the present invention, if necessary, the following general formula (a)
Nitrogen-containing compounds represented by (f) to (f) can be added.

[0114]

[Chemical 57] In the formula, X represents a hydrogen atom or a hydroxyl group; R ₃₂ , R ₃₃ and R ₃₄ are a hydrogen atom, a chlorine atom or a carbon number of 1 to 6 respectively.
Represents an alkyl group of

[0115]

[Chemical 58] In the formula, R ₃₅ and R ₃₆ are each a hydrogen atom or a carbon number of 1 to
Represents an alkyl group of 6,

[0116]

[Chemical 59] 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,

[0117]

[Chemical 60] 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,

[0118]

[Chemical formula 61] 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,

[0119]

[Chemical formula 62] In the formula, R ₄₄ and R ₄₅ are each a hydrogen atom or a carbon number of 1 to
It represents 12 alkyl groups, 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, the compound etc. which are shown by a following formula can be mentioned.

[0123]

[Chemical 63]

[0124]

[Chemical 64] Examples of the compound represented by the general formula (d) include compounds represented by the following formula.

[0125]

[Chemical 65]

[0126]

[Chemical 66] Examples of the compound represented by the general formula (e) include compounds represented by the following formula.

[0127]

[Chemical 67] In addition, examples of the compound represented by the general formula (f) include compounds represented by the following formula.

[0128]

[Chemical 68] Among the above-mentioned nitrogen-containing compounds, particularly preferable are the benzotriazoles represented by the general formula (a).

The nitrogen-containing compound can be used in the photocurable resin composition for forming the photosensitive coating layer of the resist of the present invention in one kind or in a combination of two or more kinds. The amount can be generally in the range of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the minute.

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 present invention, a protective film may be laminated on the adhesive photosensitive coating layer, if necessary. For example, when the film resist is stored in a roll form, it is preferable to stack a protective film.

Examples of the protective film include general release paper, polyester film, polyethylene film,
Examples thereof include polypropylene film and Teflon film.

In the film resist of the present invention, it is important that the adhesion between the layers is sufficiently controlled, and the adhesive strength between the layers (JIS Z 0287-19).
180 ° peel strength according to 80) is generally 1.5 to 10 g / cm, preferably 1.5 to 5 g / cm between the supporting film and the non-photosensitive layer; usually 20 g / cm between the non-photosensitive layer and the photosensitive layer. cm or more; further, the distance between the photosensitive layer and the protective film can be generally 3 g / cm or less, preferably 2 g / cm or less.

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

The method for producing the film resist of the present invention includes, for example, (a) a non-photosensitive coating layer is uniformly coated on a supporting film, dried, and then a photosensitive coating layer is uniformly coated and dried. (B) Laminating a protective film on the photosensitive film layer of the film prepared in (a) above; (c) Applying a non-photosensitive film layer on a supporting film and drying, and applying a photosensitive film layer on the protective film. After drying, the non-photosensitive coating layer and the photosensitive coating layer are laminated together.

And the like.

For exposure and development of the film resist of the present invention, for example, first, the adhesive photosensitive coating layer is exposed,
Stack them on the substrate so that they are in contact with each other, and press-bond with a hot roll. Then, the support film is peeled off, the patternwise exposure is performed through the non-photosensitive coating layer by a direct drawing method, and after the exposure, the non-photosensitive coating layer and the unexposed portion are developed with a developing solution that selectively dissolves. You can

The substrate is a metal or inorganic or organic substrate on which a metal foil is laminated or a metal is vapor-deposited, and when an etching process is required, an etching liquid capable of etching the metal is used to expose the metal exposed by the above-mentioned development. A portion can be removed by etching.

An etching pattern can be obtained by stripping the remaining resist film on the metal with a stripping agent (for example, acid, alkaline aqueous solution, solvent, etc.).

When the substrate is a metal or inorganic or organic substrate on which a metal foil is laminated or a metal is vapor-deposited and etching processing is required, the metal surface exposed by developing as described above is used. After applying plating such as solder to the resist, the resist film is peeled off with a peeling agent, and then the exposed metal is removed with an etching liquid that selectively etches the metal.
It is also possible to obtain an etching pattern.

[0142]

[Effect] The film resist of the present invention described above has a high resolution, does not deteriorate in photosensitivity due to oxygen, can be applied to a through-hole substrate, and has an excellent fine image pattern forming ability by a direct drawing method. It can be effectively used in the fields of printed circuit boards, metal microfabrication, and the like.

[0143]

The present invention will be described in more detail with reference to the following 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, acrylic acid 55 parts, azobisisobutyronitrile 2
11 parts of the 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 consisting of 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., and 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 of 7 parts at 60 ° C. The reaction was carried out for a time to obtain a photocurable resin solution 2 (0.67 mol / kg resin of quaternary ammonium salt, 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 as. 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, unsaturation degree: 3.1 mol / kg resin, resin Tg 0 ° C., solid content 56 %) Was obtained.

Production Example 4 Methyl methacrylate 45 parts Acrylic acid 55 parts Azobisisovaleronitrile 1.5 parts A 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.

[0148]Production Example 5 Ethyl acrylate 45 parts Methyl methacrylate 25 parts n-Butyl acrylate 15 parts Acrylic acid 15 parts Azobisisobutyronitrile 2 parts Except for using as a monomer mixture liquid
An acrylic resin solution was obtained in the same manner as in Production Example 1. to this
Non-photosensitive resin solution (acid value)
2.1 mol COOH / kg resin, resin Tg 9 ° C, solid content
52%). Example 1 In the photocurable resin solution 1 obtained in Production Example 1, resin solid content 10
The photopolymerization initiator (3,3 ', 4,4'-tetra (t
ert-isobutylperoxycarbonyl) benzopheno
5 parts and a spectral sensitizer (A-
1) Dissolve 1 part in 20 parts isobutyl acetate and add
Photosensitive composition 1 was prepared. Tin this photosensitive composition 1
Apply it to a plate to a dry film thickness of 20 μm and
The glass transition temperature of the product dried for 0 minutes was measured. result
Is shown in Table-1.

[0149]

[Chemical 69] On a polyethylene terephthalate film having a film thickness of 100 μm, polyvinyl alcohol (polymerization degree 1700, Tg 6
5 ° C, oxygen permeability 2 × 10 ^-14 cc · cm / cm ² · se
A 12% aqueous solution of c · cmHg) was uniformly applied so as to have a dry film thickness of 3 μm, and dried at 80 ° C. for 10 minutes to form a non-photosensitive coating layer. Next, the photosensitive composition 1 was applied thereon so that the dry film thickness was 15 μm, and the composition was dried at 80 ° C. for 10 minutes.
After drying for a minute, a photosensitive coating layer was formed to obtain a film resist 1. The interlayer adhesion of this film was measured and
Shown in 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, and 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
Film resists 2 to 4 were obtained in 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 interlayer adhesive strengths of the film resists 2 to 4 are shown in Table-2. In addition, in Example 4, a silicone-based release paper was laminated as a protective film on the surface of the photosensitive coating layer.

Comparative Example 1 A 100 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.

Comparative Example 2 A film resist 6 was obtained in exactly the same manner as in Example 2 except that the photosensitive composition 5 having the composition shown in Table 1 was used to form the photosensitive film layer. The glass transition temperature of the photosensitive composition is shown in Table-1, and the interlayer adhesive strength of the film resist 6 is shown in Table-2.
It was shown to.

Comparative Example 3 A film resist 7 was obtained in exactly the same manner as in Comparative Example 1 except that the photosensitive composition 6 having the composition shown in Table 1 was used. The glass transition temperature of the photosensitive composition 6 is shown in Table-1, and the interlayer adhesive strength of the film resist 7 is shown in Table-2.

Comparative Example 4 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 to obtain a film resist 8 in exactly the same manner as in Example 1. The interlayer adhesive strength of the film resist 8 is shown in Table-2.

[0155]

[Table 1] Abbreviations or structures in Table-1 are as follows.

Note 1) Iron-allene complex (F-1)

[0157]

[Chemical 70] Note 2) Titanocene compound (T-1)

[0158]

[Chemical 71] Note 3) Spectral sensitizer (A-1)

[0159]

[Chemical 72] Note 4) Spectral sensitizer (A-2)

[0160]

[Chemical 73] Note 5) Spectral sensitizer (A-3)

[0161]

[Chemical 74]

[0162]

[Table 2] Application Examples 1-11 Thickness 1.6 mm with 0.4 mmφ conductor-flue hole
On the copper-clad laminate having a copper thickness of 50 μm, the film resists 1 to 8 obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were placed so that the photosensitive coating layer was in contact with the copper surface (the film resist 4 was a protective film). Was peeled off and thermocompression-bonded at 90 to 100 ° C.
Next, the support film is peeled off, and the film resist 5
As it is) Argon ion laser (wavelength 488n
m) Test pattern (line (μm) / space (μm) = 200/200, 150/150, 1 with direct drawing machine
00/100, 80/80, 60/60, 50/50,
40/40, 30/30, 20/20) and the through hole opening and the land forming portion were exposed under the exposure conditions shown in Table-3. Next, development is performed with a predetermined developing solution and conditions (the film resist 5 is formed by removing the supporting film before development). After etching with ferric chloride, the resist is removed with a predetermined removing solution to form a circuit pattern and The protection status of the through hole was observed. The results are shown in Table-3.

[0163]

[Table 3] Comparative Example 5 The photosensitive composition 1 was applied to the above copper-clad laminate to give a dry film thickness of 15
After being uniformly coated so as to have a thickness of μm, it is dried at 80 ° C. for 10 minutes, and then the same polyvinyl alcohol aqueous solution as that for forming the non-photosensitive coating layer of Example 1 is applied thereon to give a dried film thickness of 3 μm. And then dried at 80 ° C. for 10 minutes, and then exposed, developed, etched under the same conditions as in Application Example 1.
Processing such as peeling was performed to obtain a circuit pattern. The resolution of the circuit pattern was 40 μm / 40 μm, but the protection status in the through hole was poor.

Claims (10)

[Claims] 1. A non-photosensitive coating layer having a film thickness of 1 to 5 μm, which is formed on a support film, is soluble in a developing solution, has an oxygen barrier property, and is substantially not tacky at room temperature, A film resist for direct writing, comprising a photosensitive coating layer provided on the non-photosensitive coating layer and having an adhesive property at room temperature. 2. The non-photosensitive coating layer has a glass transition point of 20.
℃ or more, oxygen permeability 5 × 10 ^-12 cc · cm /
The film resist for direct writing according to claim 1, which has a cm ² · sec · cmHg or less and is soluble in water or an aqueous developer. 3. The non-photosensitive coating layer comprises polyvinyl alcohol, a mixture of polyvinyl alcohol and a vinyl acetate polymer, a partially saponified product of polyvinyl acetate, or a mixture of a partially saponified product of polyvinyl acetate and polyvinyl alcohol. A film resist for direct writing according to item 1 or 2. 4. The film resist for direct writing according to claim 1, wherein the glass transition point of the unexposed film of the photosensitive film layer is 5 ° C. or lower. 5. The direct drawing film resist according to claim 1, wherein the photosensitive coating layer is curable by a visible light laser. 6. The direct writing film resist according to claim 1, further comprising a protective film laminated on the photosensitive film layer. 7. The resist film according to claim 1 is brought into close contact with the photosensitive coating layer so as to come into contact with the object to be etched, the supporting film is peeled off, and then exposed in the atmosphere by a direct drawing method, and then exposed. Develop and etch,
An etching method characterized by removing the resist film on the obtained pattern. 8. The resist film according to claim 1 is brought into close contact with the photosensitive coating layer so as to come in contact with the material to be etched, the supporting film is peeled off, and then exposed in the atmosphere by a direct drawing method, and then exposed. An etching method characterized by developing, soldering the exposed part, peeling off the resist film, and removing the exposed part to be etched with an etching solution. 9. The protective film of the resist film according to claim 6 is peeled off, and the photosensitive film layer is brought into close contact with the material to be etched so as to come into contact with it, and the support film is peeled off. Exposure, then development,
Etching method characterized by performing etching and peeling the resist film on the obtained pattern. 10. The protective film of the resist film according to claim 6 is peeled off, the photosensitive film layer is brought into close contact with the material to be etched so as to come into contact with the work to be etched, and the supporting film is peeled off. Etching method, which comprises exposing the exposed portion to light and then developing it, soldering the exposed portion, peeling off the resist film, and removing the exposed portion to be etched with an etching liquid.