JPH012037A - photosensitive composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel heat-resistant photosensitive composition.

[Conventional technology]

In recent years, development of heat-resistant photosensitive polymer materials for use in electronic and optical materials has become active.

For example, development of surface protective films such as junction coat films and α-ray shielding films, insulating films for semiconductor elements such as interlayer insulating films for multilayer wiring, insulating films for multilayer printed circuit boards, and protective films for various printed circuit boards. is being actively considered.

Heat-resistant photosensitive compositions used in these applications include, for example, mixtures of polyamic acid, which is a polyimide precursor, and photosensitive compounds, or polymers in which active functional groups such as double bonds are introduced into the side chains of polyamic acid esters ( A composition is known in which a photopolymerization initiator and a crosslinkable hexamer are added to a photosensitive polyimide precursor (photosensitive polyimide precursor), and a crosslinked structure is formed by light irradiation.

(Special Publication Akira! Ku/Gu! 7 Tata Publication, Special Publication Akira!!-3θ
The composition is a basic composition of heat-resistant polymer materials for lithography, typified by photosensitive polyimide, and To form an image using , a solution of polymer and additives is applied onto the substrate to be imaged by roll coating, spin cord, curtain coating, etc., dried to form a resist coating, and then exposed to light. , it is generally developed to form a pattern, and then heat-treated to convert it into an imide structure.

[Problem that the invention seeks to solve]

When this photosensitive polyimide is used as a solution film, isolated polymer powder and other additives are often dissolved in a solvent. However, there is a problem in that isolation and purification of this polymer from the synthesis reaction solution requires many steps. In addition, a composition consisting of a mixture of a polyamic acid and an amine compound having an active functional group can be prepared by adding an additive to a polymer solution (2). On the other hand, it has a high viscosity and cannot increase the solid content concentration, so it is not suitable for forming thick films.In addition, these photosensitive methods Polyimides generally require high temperatures of about θθ℃ during heat treatment for imidization, so depending on the application, the base material or the element to be protected may not have sufficient heat resistance. It is preferable that the structure can be converted into an imide structure at a low temperature of 300° C. or lower.

In addition, since a high boiling point solvent is generally used for photosensitive polyamide foam, there is a problem that drying time becomes long when forming a thick film, and therefore dry film formation is being considered.

(Japanese Patent Application Laid-open No. 20104-7073/) Furthermore, solder resist films are known as heat-resistant film resist films, but (see JP-A No. 20104T4), these are generally It is a composition consisting of an acrylate polymer, a monomer, etc., and has the problem that the film after photocuring is brittle and cannot be used on flexible substrates such as flexible printed circuit boards.

[Means for solving problems]

In view of the above circumstances, the present inventors developed a photosensitive polyimide precursor composition that can be converted into a polyimide pattern with a wide range of film thickness at a relatively low temperature of 3oθ°C or lower and that can be easily produced in the form of a film or dry film. Upon investigation, the following composition was found to be suitable, leading to the present invention.

That is, the present invention has a repeating unit represented by formula (1), and upon heat treatment, the thermogravimetric decrease starting temperature is
The present invention provides a composition containing as essential components a polymer that can be converted into a polymer having a temperature of 30θ°C or higher and (1) a photopolymerization initiator.

#X＼ZfY±Z: 11) [However, in the formula,
is a divalent carbocyclic group or a heterocyclic group, Y is a covalent carbocyclic group or a heterocyclic group, Z is a bond between XY, and the ratio of Z is θ~/Q mol Zl and other 2
Of these, 90~/, t Q mot 俤 is Z, and 10
~to mot% is Z3. Further, C) R represents a group having a reactive carbon-carbon double bond. ]Here, X has 6 to 6 carbon atoms. 20 aromatic hydrocarbon groups or a group represented by Xa below can be used.

ca=o, /: X, = -CH, -1-c-1-white, u10-1-0-] CF.

Specific examples of X include the following. As Y, an aromatic hydrocarbon group having 6 to λθ carbon atoms and a group represented by Ya, Yb, or Yc can be used.

10-1-8-: R, , R4 each represents a hydrogen atom or an alkyl group having 7 to 7 carbon atoms. ] Specific examples of Y include the following, and in terms of solubility of the resulting polymer, the formula
Groups represented by are preferred.

(Yz = CH, -5-0-: R, , R, represents an alkyl group with carbon number/~B.] kC6+ (J U +2r-c = Ckit
(Ha) (a=θ, /SR,=H or CH3:
R6 represents an alkyl group or an aromatic group which may contain an oxygen atom and a nitrogen atom. ] Specific examples of Ra include -O-CH, -CH-CH2-CH=CH.

Akira etc.

Of the bond Z between X and Y, 90 ~ / Omol %,
Preferably ≦θ~koθmoz % is ZI, and among the other Z, 9θ~4tOmot46, preferably ♂0~
s o mot% is Z, lθ~6θmoz%,
Preferably, Q−jQ rnot % is Z.

The polymer of component (a) is a polymer that can be converted into a polymer having a thermal weight loss initiation temperature of 30θ°C or higher, preferably 3jO°C or higher during heat treatment. Here, the heat treatment is carried out at a temperature at which monomers, initiators, etc. can be volatilized and the polymer can be converted into a heat-resistant structure according to a practical method, and the temperature at which thermal weight loss starts is determined by a differential thermometer.

Preferred specific examples of the polymer of component (a) include, for example, polymers having repeating units represented by structural formulas P-/ and P-2.

(P-/) (P-, R) The photopolymerization initiators used in the present invention are well-known ones, such as benzophenone, methyl 0-benzoylbenzoate, g,4t'-bis(dimethylamino)benzophenone, 4t , 4t'-bis(cyamino)benzophenone, terdichlorobenzophenone, g, -benzoyl-y'-methyldiphenylketone, cyhensylketone, fluorenone, and other pentuphenone derivatives; Acetophenone derivatives such as 2-methylpropiophenone and p-1-butyldichloroacetophenone Near-hydroxychlorohexyl phenyl ketone: Dioxanthone derivatives such as thioxanthone, λ-methylthioxanthone, 2-chlorothioxanthone, co-isopropylthioxanthone, diethylthioxanthone; benzyl, Benzyl derivatives such as benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal; Benzoin derivatives such as benzoin, benzoin methyl ether, benzoin isobutyl ether; Anthraquinone derivatives such as anthraquinone, 2-t-butylanthraquinone, co-amylanthraquinone, β-chloroanthraquinone, etc. Anthrone, benzanthrone, dibenzosuberone, methylene anthrone and other anthrone derivatives, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, terazobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine 2,6-di(Z'
-Diazidobenzal)-gumethylcyclohequinanone,
λ, azides such as di(q'-diazidobenzal)cyclohexanone, /-phenyl-/, 2-butanedione-
2-(o-methoxycarbonyl)oxime, /-phenyl-propanedione-2-(o-ethquincarbonyl)
Oxime, /-phenyl-propanedione-,2-(0
-Hyzoyl)oxime, /, 2-diphenyl-ethanedione-/-(O-benzoyl)oxime, /, 3-
9 Oximes such as phenyl-propanetrione-2-(o-ethoxycarbonyl)oxime, /-phenyl-3-ethoxy-propanetrione-,2-(o-benzoyl)oxime, and Michler's ketone, Shimari'-bis( Examples include bisalkylaminobenzophenones such as (diethylamino)-benzophenone, and from the viewpoint of photosensitivity, a combination of oximes and bisalkylaminobenzophenones is preferred.

Further, compounds having reactive carbon-carbon double bonds can also be used in the composition of the present invention. Examples of these compounds include -monoethyl-xyl acrylate, co-hydroxyethyl acrylate, N-vinyl-1-pyrrolidone, carpitol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, /
, 6-hexine diol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylol Examples include methane tetraacrylate, tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, methylene bisacrylamide, N-methylol acrylamide, and those obtained by changing the above acrylate or acrylamide to methacrylate or methacrylamide.

Among these, polyacrylates having two or more acrylate groups are preferred, and from the viewpoint of photosensitivity, compounds represented by structural formula M are particularly preferred.

(p=/~20) Moreover, a sensitizer can also be added to the composition of the present invention. This sensitizer can improve the sensitivity of the film, and includes, for example, Michler's Keto 7.4t, 4t'-bis-(diethylamino)-benzophenone, 2.5-bis-(4t'-diethylaminobenzal). -Cyclopentanone, rice-bis(g'-diethylaminobenzal)-cyclohexanone, co,o-bis-(4t'-dimethylaminobenzal)-gumethyl-cyclohexanone, co,6-pisu(terdiethylaminobenzal) -coumethyl-cyclohexanone, g,4t'-bis-(dimethylamino)-chalcone, terbis-(diethylamino)-chalcone, p-dimethylaminobenzylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p- dimethylaminophenylvinylene)-benzothiazole, , 2-(p-di)f-ylaminophenylvinylene)-isonaphthothiazole, 7.3-bis-
(9'-dimethylaminobenzal)-acetone, 7.3
-bis-(terdiethylaminobenzal)-acetone,
3.3'-Carponylrubis-(7-diethylaminocoumarin), N-phenyl-N'-ethelethanolamine, N-phenyldiethanolamine, N-tolylgetanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, Examples include, but are not limited to, isoamyl diethylaminobenzoate.

Furthermore, a silane coupling agent may be added to the composition of the present invention, or a silane coupling agent may be pre-coated on the base material. This silane coupling agent is a compound that improves the adhesion of the interface between the heat-resistant polymer film of the composition of the present invention and the base material Si, inorganic insulating film, etc. Examples of these include: For example, r-aminopropylmethyldimethoxysilane, N-(β-aminoether)γ-aminopropylmethyldimethoxysilane, r-glycidoxypropylmethyldimethoxysilane, r-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxysilane Methylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, jetoxy-3-glycidquinpropylmethylsilane, N-(3-jethoxymethylsilylpropyl)succinimide, and the like. The method of use and effects of these dialcoquine silane compounds are described in detail in, for example, Japanese Patent Application No. 6θ-3♂J4tj. Furthermore, a polymerization inhibitor may be added to improve the storage stability of the solution of the composition of the present invention.

Examples of the polymerization inhibitor include hydroquinone, N
-Nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, /, cocyclohequitinediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2.6-sheet tcrt-butyl-p-methylphenol etc.

In the composition of the present invention, the content ratio of the photopolymerization initiator and the sensitizer to the polymer of component (a) is preferably θ, / to −0 weight ratio. ~/j weight aS is more preferred. Further, the content ratio of the compound having a reactive carbon-carbon double bond is preferably 20% by weight or less with respect to the polymer of component (A). When a functional dialkoxysilane compound is added and used, its content ratio is 0.0% to the polymer of component (a). Or −/θ% by weight, preferably θ,/~g% by weight. Further, the content ratio of the polymerization inhibitor is less than or equal to the ratio by weight of the polymer of component (a), preferably less than or equal to θ,7% by weight.

The polymer of component (a) of the present invention can be synthesized by the following method. That is, first, an acid anhydride represented by formula (V) and a diamine represented by formula (Vll) are reacted to form a polyamic acid, and further, a polyamic acid having a grindyl group, represented by formula (R-A) Compounds are reacted and esterified.

(x and y have the same meanings as above.) υ [d=0 or/; R3 is H or CH: R'6 represents an alkyl group that may contain an ether bond. ](R-
Specific examples of A) include glycidyl methacrylate, glycidyl acrylate, and the like.

, this synthesis method is described in JP-A-4-323.24.
It is described in detail in JP-A No. 4-33/3/1999.

The parent polymer, component (a), can also be obtained by reacting the above-mentioned polyamic acid with a compound having an isocyanate group and represented by the formula (R-B).

[R7 is an aliphatic group having 3 to 2 carbon atoms or an aromatic group; R3 is an aliphatic group having 1 to 2 carbon atoms; Ro represents H or CHl; and e is 0 or /. ] Specific examples of R-H include OO and the like, and these compounds can be obtained by reacting the corresponding diisocyanate compound with an alcohol compound having a double bond.

The solvent for the reaction is preferably an aprotic polar solvent, such as r-butyrolactone, N-methylpyrrolidone, N-acetel-cobyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, Examples include hexamethylphosphoric triamide and N-benzyl-2-pyrrolidone. Among these, N-methylpyrrolidone and N,N9 methylacetamide are preferred from the viewpoint of coating properties in subsequent steps. Moreover, as conditions for the reaction, first, an acid anhydride is dissolved in a solvent, and a solution of a diamine compound in the same solvent is added while stirring. The preferred reaction concentration is 30~! The viscous liquid produced after heat generation is stirred at room temperature for 3 to 6 hours. Next, the aforementioned Grindyl compound or
The isocyanate compound is added dropwise and stirred at a temperature of 0-90°C for 70-30 hours. The ratio of the bond type Z (Z+:Zt:'') in the resulting polymer, XZYZ..., can be controlled by the equivalent weight of these compounds to the carboxylic acid group of the polyamic acid, and the reaction temperature and time. The polymer solution obtained in this way can be used as a phenol for a photosensitive polyimide precursor by adding additives such as a photopolymerization initiator and dissolving it as it is. It can also be used by isolating and purifying it by reprecipitation method etc. and redissolving it with additives.These phenos can be coated onto the base material by spin cord, curtain coating, roll coating, etc. and dried. The drying temperature is 410 to 4tθ°C, preferably evening θ to
It is 10θ°C.

Furthermore, by adding a relatively low boiling point solvent to these phenos that azeotropes with the solvent to lower the boiling point, it can be coated as a dry film. Examples of the low boiling point solvent include cyclopentanone, cyclohexanone, and tetrahydrofuran. The support for coating is preferably transparent, has sufficient strength, and is insoluble in the solvent used, and films such as polyethylene terephthalate and polypropylene can be used. As the cover film, in addition to the above-mentioned films, films such as polyethylene can also be used.

As a dry film coating method, methods such as barcode coating, blade coating, pipe doctor blade coating, etc. can be used.

What are the drying conditions for the coated film? 6θ~ in a circulation oven at θ~/koθ℃! It's a minute. The thickness of the film that can be formed is from 7 to 700 μm, preferably from 70 μm to 70 μm.

The film thus formed is laminated together with a support film onto a substrate by heating and pressurizing. Preferable lamination conditions are as follows: using a hot roll laminator, a roll temperature of 0~/6θ°C, and a roll pressure of θ, j-
，! v-, particularly preferably 70 to 4tθ°C and 7 to 3 degrees.

These support films are peeled off before or after exposure and before development.

The thus obtained laminate with phenol and dry film is exposed through a conventional photomask.

Examples of the active light used for this removal include ultraviolet rays, X-rays, and electron beams. Among these, ultraviolet rays are preferred, and examples of the light sources include, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, Examples include germicidal lamps. Among these light sources, ultra-high pressure mercury lamps are preferred. Further, it is preferable that the exposure is performed under a nitrogen atmosphere.

Further, as a developing method, a dipping method or a spray method can be used. As a developer, r-butyrolactone, N
-Methylpyrrolidone, N-acetel-2-pyrrolidone,
Polar solvents such as α-acetyl-butyrolactone and N,N-dimethylacetamide may be used alone, or as a second component, aromatic solvents such as alcohols such as ethanol and isopropanol, toluene, and xylene may be used. A mixture of solvents such as group hydrocarbon compounds, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and methyl propionate, and ethers such as tetrahydrofuran and dioxane may be used.

Further, immediately after development, it is preferable to rinse with a solution as shown as the above-mentioned component No. 1.

The pattern thus obtained is heated in nitrogen at a temperature of //θ to 4tθθ°C, preferably θO to 300°C, in nitrogen.
It is converted into a polyimide structure by heat treatment for 5 to 3 hours, preferably 7 to 2 hours.

〔Example〕

The present invention will be specifically explained below with reference to Examples and Reference Examples.

Reference Example/3. 96.7f of 3', 4t, 4t'-benzophenone tetracarboxylic dianhydride (BTDA) was dissolved in N-methylpyrrolidone (NMP)/jOtd. After stirring this solution, 4t'-diamino-3,3',
3-. 3'-tetraetherdiphenylmethane, 4t3
．． /f and g.

Dacyamino-3,3'-dimethyl-3,! '-diethyldiphenylmethane39. A 232 ml solution of tf in NMP was added. The reaction solution was stirred for several hours while being cooled in a water bath. '12.79 glycidyl methacrylate was added to the resulting amic acid solution and stirred at 7θ°C for 26 hours. The obtained solution will be referred to as Polymer A solution. This polymer was isolated by a partial reprecipitation method and its acid value, IH-NM
Structural analysis using R spectrum and infrared absorption spectrum revealed that λjmot of the bond between the acid component and the diamine component.
% is amic acid ester, 4t7 mob is amic acid, and 2r mob is imidized. Further, after heat-treating this polymer powder at 300° C. for 1 hour, the thermogravimetric decrease starting temperature was measured at a temperature increase rate of 10° C./min in a nitrogen stream using a differential thermal balance and found to be 3jO° C.

Reference example λ Dissolve pyromellitic anhydride tg t, 4tf in dimethylacetamide (DMAC) 200-, add a DMAC 5,2θ-solution of g, 4t'diamino-3,3-j,j'-tetraethediphenylmethane, I stirred it for a while. Next, glycidyl methacrylate/ , t, 3 f
DM Ac♂0-solution was added thereto, and the mixture was stirred at 70° C. for 74 hours. The obtained solution will be referred to as Polymer B solution. Structural analysis in the same manner as above revealed that among the bonds between the acid component and the diamine component, 4tJ mot ts is an amic acid ester, 4to mob is an amic acid, and / 7
It was found that mot91p was imidized.

Further, the temperature at which thermal weight loss started after heat treatment at 300°C for 2 hours was 34tθ°C.

Reference Example 3 A DMAC/θθ+nl solution of diaminomeshiterenko ♂t was added to a DMAC/θθ+nl solution of BTDA64t, 4tt and stirred for 9 hours. Next, glycidyl methacrylate 522 was added and stirred at 70°C for 71 hours.

This solution will be referred to as Polymer C solution.

When the structure was analyzed in the same manner as above, 3rmoz% of the bond between the acid component and the diamine component was an amic acid ester,
37 mob 'A is an amic acid and J j mob
It turned out that the person in charge was imidized. Further, the thermogravimetric decrease starting temperature after heat treatment at 300°C for 2 hours was 340°C.

Reference Example 3.3-q, terbiphenyltetracarboxylic dianhydride ♂♂, 3f DMAC, 3.3'- in 20θ-solution
A DM Ac 300 td solution of diaminog, dimethyl-3,3;'-diethyldiphenylmethane was added and stirred for an hour. next! ! , 3f of glycidyl methacrylate was added, and the mixture was stirred at 70° C. for a waiting period of 30 minutes.

This reaction solution was added dropwise to 1 liter of ethanol/water (20: J'θ volume) with stirring, and the resulting precipitate was separated and dissolved in 1/l of tetrahydrofuran.

This solution was added dropwise to 9 tons of water while stirring, and the resulting polymer powder was collected by filtration. This will be referred to as Polymer D.

When the structure was analyzed in the same manner as above, 2 j mot% of the bond between the acid component and the diamine component was an amic acid ester, 9θ mot% was an amic acid, and 3 j mot% was an amic acid ester.
was found to be imidized. Also, 2 at 300℃
The thermogravimetric decrease starting temperature after the time heat treatment was 33-, jt°C.

Next, the names and abbreviations of the additives used in the examples of the present invention are shown in Table/.

(Leaving space below) Table / - (1) Initiator table / - (21 seven squares) Table / - (8) Sensitizer table / - (41 Silane coupling agent examples / Polymer solution A /36?, start agent I −/2,
s f,■-Evening to evening 1, Nanatsuma-M-/Gi.

Sensitizer S-7 at θ, 752 and cyclopentanone at 2
♂, ri? The mixture was added and dissolved by stirring. This solution was coated onto a 2♂μm thick polyethylene terephthalate (PET) film using a blade coater.
After drying for 90 minutes using a circulating oven at .degree. C., a dry film with a thickness of 3 .mu.m was obtained. This dry film was heated using a hot roll laminator (AL-70 manufactured by Asahi Kasei Corporation) at a roll temperature of 10°C and a roll pressure of 2 Ki.
! , a flexible printed circuit board (electrolytic copper foil/♂μ
m/polyimide base film/2. ! μm), P
It was laminated with the ET film facing up. Next (2 PE
The T film was exposed for minutes through a photomask using an ultra-high pressure mercury lamp (exposure intensity ♂mW/ad).

Next, peel off the PET film and open the 7θ film at 70°C.
Heat treated for 1 minute. Next, this board was developed with a developer of NMP/xylene/water (tO: 4tO: 3 volumes) and rinsed with isopropyl alcohol, and the pattern of three pins (space width/4t0μm) had a sharp resolution. was formed with. This substrate was placed in a nitrogen stream for 23 minutes.
A heat treatment was performed at 0° C. for 7 hours to convert it into a 29 μm thick polyimide pattern. The dielectric constant (ε) of the film after heat treatment was 3.2. Next, in order to solder the copper wiring terminals on the board on which this cover layer was formed, after degreasing and fluxing the board, it was immersed in a solder bath of 1.2gθ℃ for 3θ seconds, and the exposed copper wiring terminals were soldered. No delamination or blistering of the cover layer was observed. Also, this board! Although the cover layer was bent 20 times, no breakage or cracks occurred in the cover layer.

Example copolymer solution B/791 with 3.6 initiator I-2
f, I-4/, j f, monomer M-2 at 39°, sensitizer S-, 2, 2f, silane coupling agent C-//, j f were dissolved. This solution was spin-coded onto a glass substrate (4 f inch square, /w thickness) and dried in a circulating open environment at 70° C. for 7 hours to form a 20 μm thick layer (two layers).

This substrate was exposed through a photomask using an ultra-high pressure mercury lamp.
Exposure was made for a minute. Next, after heat treatment at 7θ℃ for 7θ minutes,
It was developed with r-butyrolactone (r-BL)/xylene (/:/vol) developer and rinsed with xylene. The resulting pattern was heat-treated at 300° C. for 7 hours in a nitrogen stream to convert it into a 13 μm thick polyimide pattern.

Example 3 Initiator I-3 was added to polymer solution CItxt at 3f%l-
s /, 2 f , monomer M-j j2, sensitizer S-
3/f and silane coupling agent C-, 2/, J
-f was added and dissolved. Spread this solution onto a silicon wafer (
3 inches) Spin code on top! It was dried for 30 minutes in the open circulation at θ°C and laminated to a thickness of 16 μm. Next, this wafer was exposed to light for 2 minutes using an ultra-high pressure mercury lamp through a photomask. Next, it was developed with a developer of NMP/isopropyl alcohol/quinolene/water (33:33:33:j volume) and a rinsing solution of isopropyl alcohol/xylene (near volume). The obtained pattern was 1.2! It was heat-treated at θ° C. for 7 hours to convert it into a polyimide pattern with a thickness of 72 μm.

Example dapolymer D rot, initiator kneader 4tf, I-6
/J f , monomer M-g 11. Sensitizer S-g/and silane coupling agent C-3, λt, NMP
, 4t/r and cyclopentanone 4t/2. This solution was coated with P using a blade coater.
It was coated onto an ET film, dried at 70° C. for 30 minutes, and laminated to a thickness of 30 μm. This film laminate is used as a flexible printed circuit board (rolled copper foil 3μm/polyimide base film 2μm) with a copper wiring pattern formed thereon.
m) was laminated using a hot-low optical laminator (AL-70') (roll temperature: 720°C, roll pressure: 3 (wrapping, feed speed: 0.6 m, 7 min). Next, ultra-high pressure was applied from above the PET film through a photomask. By mercury lamp!
Exposure was made for a minute. After that, peel off the P13T film and
Heat treatment was performed in an oven at 0°C for 3 minutes. This board is NM
When developed with a P/xylene/water (4tj:jj near volume) developer, a 720 μm8 diameter hole was formed with sharp resolution. This substrate was placed in a nitrogen stream for 2
A heat treatment was performed at 00° C. for 1 hour to convert it into a polyimide pattern with a thickness of 3 fμm. The dielectric constant (ε) of the film after heat treatment was 3.4t. Next, soldering was performed in the same manner as in Example, but no delamination or blistering of the cover layer was observed. Further, even though this substrate was bent 20 times at 10 mB, no breakage or cracking of the cover layer occurred.

Patent applicant: Asahi Kasei Industries, Ltd. Representative patent attorney Nozaki Kushiya

Claims (1)

[Scope of Claims] A) A polymer having a repeating unit represented by the general formula (1) and capable of being converted into a polymer having a thermal weight loss onset temperature of 300°C or higher upon heat treatment, and b) Photopolymerization. A composition containing an initiator as an essential component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) [However, in the formula, X is a tetravalent carbocyclic group or a heterocyclic group,
Y is a divalent carbocyclic group or heterocyclic group, Z represents a bond between XY, 90 to 10 mol% of Z is Z_1, and 90 to 40 mol% of other Z is Z_2, 10 to 60 mol% is Z_3. Also, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Z_1) (Z_2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Z_3) R represents a group having a reactive carbon-carbon double bond. ]