JPS59201044A - Heat resistant film photoresist laminate - Google Patents

Abstract

PURPOSE:To improve the adhesion between an upper layer resist and lower layer resist and heat resistance by compounding a specific amt. of a tack imparting agent with the resist in the laminate of the film photoresist consisting of the upper layer resist and the lower layer resist. CONSTITUTION:A laminate is formed of an upper layer resist and a lower layer resist. The lower layer resist is formed of a compsn. consisting essentially of the cyclized matter of a butadiene polymer. The upper layer resist is formed of the compsn. contg. 100pts.wt. a polymer or copolymer of a mono-olefin unsatd. compd., 5-100pts.wt. a multifunctional photopolymerizable unsatd. compd. having photopolymerizable double bonds in the molecule, a photocrosslinking agent, a photosensitizing agent, a photopolymn. initiator, etc. A track imparting agent is compounded with the upper layer resist and lower layer resist of the laminate of the photoresist constituted in such a way at a rate of 0.1-50pts.wt. in 100pts.wt. the polymer or copolymer of the cyclized matter of the butadiene polymer or the polymer of the mono-olefin unsatd. compd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention 1 relates to a film photoresist laminate having excellent heat resistance. For more details, please see above.

The present invention relates to a heat-resistant film photoresist laminate with good adhesion between cyst and lower resist layer.

Conventionally, so-called solder resists used in the printed wiring board industry have the role of hiding unnecessary parts of printed wiring board circuits and preventing short circuits caused by solder bridges between circuits, and at the same time, they also serve to prevent unnecessary soldering. It prevents weight increase due to adhesion, and its surface coating is used as an insulating protective film for circuits.

As such resists, liquid resists and film resists are commercially available. For the former, thermosetting resins such as epoxy resins, epoxy-melamine resins, epoxy urea resins, alkyd-melamine resins, photosensitive acrylate modified resins, etc. are used.

Liquid resist is difficult to apply thickly, and
There are drawbacks such as low dimensional accuracy of the formed pattern. Moreover, as the spacing between the circuits becomes narrower, it becomes difficult to apply resist between the circuits, making it impossible to use it for high-density printed wiring boards.

On the other hand, the film resist is, for example, "Hitachi Photosensitive Solder Resist Film Photo" manufactured by Hitachi Chemical Co., Ltd.
c 5R-1000”, DuPont 6s;t, ) y (Ris-ton) 730F
R'', Dynachem's 6-laminar SM', etc. are known.These are all made from acrylate polymers, acrylate monomers, storage stabilizers, dyes, and photopolymerization initiators. However, since these compositions contain a large amount of acrylate monomer, the film resists produced from them are soft and sticky, and are difficult to bond to support films such as polyester films. The resist composition must be handled as a structure sandwiched between a protective film such as a polyolefin film and a protective film such as a polyolefin film.Also, even in such a structure, if stored at high temperatures for a long period of time, the resist composition will break down into the support. This has the disadvantage that it protrudes from both sides of the film, resulting in poor opening properties and thickness dimensional accuracy of the film.

Furthermore, since the photosensitive layer is sticky, the photomask cannot be placed in close contact with the photomask during image printing, and printing must be done through a support film, which not only makes it difficult to obtain clear images, but also makes the film brittle after photocuring. , it has drawbacks such as the image being easily chipped. Furthermore, it has the fatal drawback of insufficient heat resistance, which is an important property for solder resists.

As a result of intensive studies to improve the shortcomings of these commercially available film photoresists, the inventors first discovered that (a) a specific amount of a polymer or copolymer of a monoolefinically unsaturated compound, (b) a specific amount of A polyfunctional photopolymerizable unsaturated compound having at least two or more photopolymerizable double bonds in the molecule, (
e) An upper layer resist consisting of a composition containing at least one selected from a photocrosslinking agent, a photosensitizer, and a photopolymerization initiator as an essential component, and a composition whose main component is a cyclized product of a butadiene-based polymer. It has been found that the above-mentioned drawbacks can be overcome by forming a structure in which the resist layer is laminated on a lower resist layer consisting of the following.

However, this film photoresist has poor adhesion between the upper layer resist and the lower layer resist, and when laminating it on a solid surface while peeling off the support film used in producing the film photoresist and the protective film laminated for storage, It has been found that if the usage conditions are incorrect, there is a risk of delamination between the upper resist layer and the lower resist layer.

As a result of further extensive research, the inventors discovered that this problem could be solved by adding a tackifier to the film photoresist, and thus arrived at the present invention. That is, the gist of the present invention is to provide (A) a lower resist composed of a composition containing a cyclized product of a butadiene polymer as an essential component, and (B) a polymer or copolymer of (a) a monoolefinically unsaturated compound. 100 parts by weight, (b) 5 to 100 parts by weight of a polyfunctional photopolymerizable unsaturated compound having at least two or more photopolymerizable double bonds in the molecule, (c) photocrosslinking agent, photosensitizer, and photopolymerization A lower layer resist of a film photoresist laminate and/or an upper layer resist made of a composition containing at least one type of initiator.
Alternatively, add a tackifier to the upper resist layer in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the cyclized product of a butadiene polymer or the polymer or copolymer of a monoolefinic unsaturated compound.
The heat-resistant film photoresist laminate is characterized in that it is blended in parts by weight.

The above tackifier is added to the lower resist layer as follows:
most effective. However, the purpose can be sufficiently achieved even if it is added to the upper resist layer. Therefore, there is no problem even if the tackifier is added to both the upper resist layer and the lower resist layer.

In the present invention, tackifiers include natural resins such as rosin and dammar, modified rosins such as polymerized rosins and partially hydrogenated rosins, derivatives of rosins and modified rosins such as glycerin ester rosins and pentaerythritol ester rosins, α - polyterpene resins such as pinene or β-pinene polymers and dipentene polymers, terpene modified polymers such as terpene-phenol copolymers and α-pinene-phenol copolymers, fats such as olefin and diolefin polymers; family hydrocarbon resins, cyclopentadiene resins, aromatic petroleum resins,
Phenolic resins such as alkylphenols and modified phenols, alkylphenol-acetylene resins,
Examples include styrene resin, xylene resin, coumaron-indene resin, and vinyltoluene-α-methylstyrene copolymer resin.

Among these tackifiers, tackifiers that do not have a functional group and do not have an isoprene skeleton, such as styrene resin, coumaron-indene resin, Aromatic petroleum resins are preferred, and coumaron-indene resins and aromatic petroleum resins are particularly preferred. These tackifiers can be used alone or in combination of two or more.

In the present invention, the tackifier is 0.1 to 50 parts by weight per 100 parts by weight of the cyclized product of a butadiene polymer or the polymer or copolymer of a monoolefinically unsaturated compound.
Parts by weight, preferably 0.5 to 30 parts by weight, are added to the lower resist or upper resist. If the amount of the tackifier added is less than 0.1 part by weight, the effect of preventing delamination will be small, and if the amount added exceeds 50 parts by weight, the performance as a solder resist such as heat resistance and electrical properties will deteriorate. descend.

The lower resist used in the present invention preferably contains a composition containing at least one selected from (1) a cyclized butadiene-based polymer and (2) a photocrosslinking agent, a photosensitizer, and a photopolymerization initiator. This is a film photoresist formed into a film. However, if it is a film photoresist mainly composed of a cyclized butadiene-based polymer, it is not limited to the above.

The above-mentioned butadiene-based polymer cyclized product is not particularly limited, but
It is desirable that the molecular weight of the butadiene polymer or butadiene copolymer as a raw material, the cyclization rate and the intrinsic viscosity [η] of the butadiene-based polymer cyclized product are within specific ranges.

In addition, examples of the copolymerized monomer of the butadiene copolymer include vinyl aromatic compounds such as styrene and α-methylstyrene, and monoolefin compounds such as ethylene and propylene.

That is, the weight average molecular weight of the raw material butadiene polymer or butadiene copolymer is 30.000 to 300.
, 000 is preferred; if the molecular weight is less than 30,000, when used as a film, the image obtained by photocuring will be brittle;
If it exceeds 00, a high temperature is required when laminating the film on the substrate, which may cause thermal fogging of the film.

In addition, 3Ji of butadiene-based polymer cyclized product (with a ratio of 40
A range of 70 to 70 is good; if the cyclization rate is less than 40, the fridien-based polymer cyclized product exhibits comb-like properties and may protrude from both sides of the support film during storage, and if the cyclization rate is less than 70,
If it exceeds 0q6, the flexibility of the film decreases, making it particularly unsuitable for lamination on copper-clad laminates.゛Furthermore, the intrinsic viscosity lume of A-tadiene-based polymer monkey compound and its photocured portion are brittle and cannot withstand use, [η))ivx'-
, exceeds 0.7, there is a drawback that the film thickness becomes uneven.

Among the butadiene-based polymer cyclized products within the above range, the cyclization rate (DC) of the cyclized product and the molecular weight (MW) of the raw material butadiene polymer or butadiene copolymer are as follows (I
) to (II), the heat resistance and storage stability of the lower resist will be even better.

The above-mentioned butadiene-based polymer cyclized product is obtained by dissolving a butadiene polymer or a butadiene copolymer in a solvent such as an aromatic hydrocarbon, and then cyclizing it with an organoaluminum compound and a catalyst such as an organohalide. Specifically, Special Publications No. 48-29879 and No. 53-1318.
It can be obtained by the method described in JP-A-48-66684 and the like.

The photocrosslinking agent, photosensitizer, or photopolymerization initiator suitably added to the above-mentioned butadiene-based polymer cyclized product includes:
Examples include: As photocrosslinking agents, 2,6-bis(4'-azidobenzal)cyclohexanone, bis(4-azidobenzal)acetone, 4,4'
-Azide compounds such as diazidostilbene and p-azidobenzalacetophenone; as photosensitizers, p, p
'-: F tramethyldiaminobenzophenone, benzophenone, anthraquinone, 1,2-benzanthraquinone, 2-methylanthraquinone, carbonyl compounds such as bioanthrone, 5-nitroacenaphthene, α-nitronaphthalene, 2-nitrofluorene, etc. nitro compounds, thioxanthone compounds such as 2,4-dimethylthioxanthone; as photopolymerization initiators, benzoin,
Benzoin compounds such as hentin methyl ether, pensoin isoglobil ether, benzoin dimethyl ketal, acetophenone compounds such as α,α′-dimethoxyα-phenylacetophenone, α,α′-jethoxyacetophenone, and sulfur such as diphenyl disulfide. Compounds can be mentioned. These compounds are
It is preferably used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the cyclized butadiene polymer, but the maximum effect is obtained when it is used in an amount of 0.5 to 5 parts by weight.

Furthermore, it is preferable to add a storage stabilizer to the lower resist NC. Examples of storage stabilizers include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol),
．． Alkylphenol compounds such as 2'-methylenebis(4-ethyl-6-t-butylphenol), 2,6-di-t-butyl-p-cresol; phenyl-β-
Aromatic amine compounds such as naphthylamine, diphenyl-p-phenylenediamine, phenylisopropylphenylenediamine, etc.; dilaurylthiodipropionate, 4,4'-thiobis(6-t-butyl-m-cresol), 2( 3゜5-di-t-butyl-4-hydroxyanilino)-4,6-bis(N-octylthio)-1
, 3,5-triazine, etc., and these are preferably added in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the cyclized butadiene polymer.

The polymer or copolymer of a monoolefin-based unsaturated compound (hereinafter referred to as an olefin-based polymer) used in the upper resist layer can be easily produced by a conventional polymerization reaction. There is no particular restriction on the molecular weight of these substances, but those that are liquid at room temperature have the disadvantage of being difficult to form into a film resist, and those with extremely high molecular weights are difficult to dissolve in a developer, so they cannot be used as resists. This is not preferable because it is difficult to obtain high resolution in this case. Preferably, weight average molecular weight is 30,000 to 1,000
, 000, especially from 50,000 to 800,000.

Examples of the olefin polymer used in the present invention include aromatic hydrocarbon polymers such as polystyrene, polyα-methylstyrene, poly(styrene-α-methylstyrene), polyvinyl chloride, polyvinylidene chloride,
Halogenated hydrocarbon polymers such as poly(vinyl chloride-vinylidene chloride), oxyester polymers such as polyvinyl acetate, polyvinyl propionate, polyvinyl methyl ether, polyacrylic acid, polymethacrylic acid, polyacrylic Methyl acid, polymethyl methacrylate, poly(
Acrylic polymers made of acrylic acid or methacrylic acid or esters thereof such as methyl methacrylate-styrene); nitrogen-containing polymers such as polyacrylonitrile, polyacrylamide, polyN-vinylcarbazole, and polyN-vinylpyrrolidone; Examples include polyethylene, polypropylene, poly(ethylene-propylene), and the like. Among these, preferred are acrylic polymers, particularly preferred are polymethyl methacrylate or a copolymer obtained by copolymerizing 50 weight or more of methyl methacrylate.

The polyfunctional photopolymerizable unsaturated compound to be combined with the olefinic polymer is one having at least two or more intramolecular pressure photopolymerizable double bonds, such as ethylene glycol diac I) L/-), ethylene glycol diesters of acrylic acid and methacrylic acid, such as dimethacrylate;
Triesters of acrylic acid and methacrylic acid such as trimethylolethane trimethacrylate and trimethylolethane trimethacrylate, and tetraesters of acrylic acid and methacrylic acid such as pentaerythritol tetraacrylate. Also, esters of acrylic acid or methacrylic acid of alkylene oxide adducts of bisphenol A, such as 2,2-bis(4-acryloxyethoxyphenyl)propane, 2,2-bis(4-
Examples include compounds obtained by reacting acrylic acid or methacrylic acid with compounds containing at least two epoxy groups, such as methacryloxyethoxyphenyl) propane, and cycloaliphatic epoxy resins and bisphene-nol A-epichlorohydrin-based epoxy resins. Can be done.

However, in order to further reduce the tackiness of the film photoresist, it is preferable that the photopolymerizable unsaturated compound has at least three or more photopolymerizable double bonds in the molecule, particularly trimethylolpropane triacrylate, trimethylolpropane Triesters of acrylic acid or methacrylic acid such as trimethacrylate, tetraesters of acrylic acid or methacrylic acid such as tetramethylolmethanetetraacrylate, and tetramethylolmethanetetramethacrylate are preferred.

These photopolymerizable unsaturated compounds are used in an amount of 5 to 100 parts by weight, preferably 20 to 30 parts by weight, based on 100 parts by weight of the olefin polymer.

Furthermore, in order to improve heat resistance, the upper resist 2 contains an amine compound 2-R-N-R3 (wherein R1, R2, and R3 may be the same or different, Each is hydrogen or an alkyl group, or two or more of them may be joined together to form a fused ring in the form of an alkylene group, but if R1, R2, and R3 are all hydrogen at the same time ) is preferably added.

Examples of the above amine compounds include primary, secondary, and tertiary monoamines and polyamines.

Also used are polyamines having two or more types of amino groups selected from primary, secondary, and tertiary in the same molecule. Monoamines include butoxypropylamine, 2-ethylhexylamine, laurylamine,
Examples include primary amines such as ethanolamine, secondary amines such as dibutylamine, diallylamine, and di-2-ethylhexylamine, and tertiary amines such as tributylamine, triethanolamine, and tri-2-ethylhexylamine. Examples of polyamines include primary diamines such as trimethylene diamine and hexamethylene diamine, N,N'-dimethylethylene diamine, and N'-dimethylethylene diamine.
, a secondary diamine such as N'-diptylethylenediamine, triethylenediamine, N.

N+N', N'-f tramethylethylenediamine, N.

Examples include tertiary diamines such as N, N', N'-tetraallyl-1,4-diamino)butane. Additionally, triamines such as diethylenetriamine, tetraamines such as triethylenetetramine, α,α′-dipyridyl, 1,4-diazabicyclo(2,2,2)octane,
Also included are heterocyclic amine compounds such as hexamethylenetetramine, imidazole, and benzotriazole. Furthermore, monomeric type amine compounds such as dimethylamine ethyl methacrylate and diethylaminoethyl methacrylate can also be used.

Among these, preferable are secondary and 3R amines of monoamines, and particularly preferable are tertiary amines of monoamines.
Class amines and polyamines are tertiary diamines. These amine compounds can not only be used alone (,2
You may use a mixture of more than one species.

The above amine compound is preferably used in an amount of 5 to 50 parts by weight, particularly preferably 10 to 30 parts by weight, per 100 parts by weight of the olefin polymer.

If the amount of the amine compound added is less than 5 parts by weight, there is no effect on improving heat resistance. Furthermore, if the amount added exceeds 50 parts by weight, the sensitivity of the resist itself decreases.

The photocrosslinking agent, photosensitizer, or photopolymerization initiator used in the upper resist layer can be the same as that used in the lower resist layer. That is, examples include azide compounds, carbonyl compounds, nitro compounds, thioxanthone compounds, benzoin compounds, acetophenone compounds, sulfur compounds, etc., and these can be added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the olefin polymer. It is preferable to use 1 part.

It is preferable to add a storage stabilizer to the upper layer resist as well.
Storage stabilizers similar to those added to the underlying resist can be used. The amount added is preferably 0.1 to 5 parts by weight per 100 parts by weight of the olefin polymer.

Depending on the use of the film photoresist laminate of the present invention, the formed image may be visually inspected, so it is desirable that the resist film itself is colored to make it easier to see. For this reason, it is preferable to color the lower layer resist and/or the upper layer resist.

Coloring can be done using dyes or pigments. Although the dye and pigment are not particularly limited, it is necessary that the image of the photocured portion remaining after development is colored. Therefore, it is preferable to use a compound that is difficult to extract with a halogenated hydrocarbon such as 1,1.1-)lichloroethane, which is a commonly used developer, and a compound that is insoluble in these developers is preferably used. Ru. As such, C,1
, Pigment Orange 14 (C, 1, 2
1165) C0 engineering, pigment Red 13 (
C,1,12395), C,1,
Pigment Blue 15 (C, 174160
)C,1,Pigment Green 7 (C,1
, 74260), phthalocyanine compounds such as C
,1,Vat Orange 3(C,1,59300
), anthraquinone compounds such as C,1,Vat
Orange 7 (C,1,71105),C,1,
Perinone compounds such as Vat Red15 (C,I 71100), C,1, VatVioret 3
(C, 1,73395), C, 1, Pigment Red 81 (C
.

1,45160), carbonium-based compounds such as C
Examples include quinacridone compounds such as 0■, 1olet 19 (C, 1,46500). These dyes and pigments are preferably added in an amount of 0.01 to 3 parts by weight per 100 parts by weight of the cyclized phtadiene polymer of the lower resist layer or the olefin polymer of the upper resist layer. The amount of dye and/or pigment added is 3
If the amount exceeds 1 part by weight, light absorption by the dye or pigment is large and sufficient photocuring is difficult to occur. Furthermore, if the amount is less than o or oi parts by weight, the coloring effect will not be sufficient.

The film photoresist laminate of the present invention is manufactured as follows. For example, at least one of (1) a cyclized phtadiene polymer, (2) a tackifier, (3) a photocrosslinking agent, a photosensitizer, and a photoinitiator, and others used as necessary. Additives made into a uniform composition using a solvent such as toluene, xylene, or tetrachloroethylene can be used as a support film such as polytetrafluoroethylene, or as a polyethylene film, polyethylene terephthalate film, or other plastic film or paper. A film tossle with a film thickness of 5 to 200 μm is coated on a support film that has been subjected to a release treatment and dried.

Next, on the lower resist layer, (a) an olefin polymer, (b) a photopolymerizable unsaturated compound, (e) a photocrosslinking agent,
A homogeneous composition is prepared by dissolving a small amount of photosensitizer and photopolymerization initiator (both one type and other additives used as necessary) in a solvent such as toluene, methyl ethyl ketone, ethyl acetate, or trichlorethylene. This is coated and dried to form an upper layer resist having a film thickness of 5 to 200 μm, and a protective film is further laminated as required.

The amount of residual solvent in this film photoresist laminate is desirably kept at 1 weight or less, and the film thickness of the film resist laminate is preferably 15 to 300 μm.

The film photoresist laminate of the present invention can be stacked so that the lower layer resist is in contact with the object to be laminated after the support film is peeled off, or after the support and protective film are peeled off, the film photoresist laminate does not change in quality and softens. temperature, i.e. 50-180C1, preferably 80
It can be easily laminated by heating to ~160C. Also, the material to be laminated should be heated at 50 to 180C.
The film photoresist laminate can also be laminated by heating it to , preferably 80 to 160 C, and then pressing it with a laminating rubber roller so that the lower resist of the film photoresist laminate comes into contact with the object to be laminated.

The film photoresist laminate of the present invention has extremely good workability, and can be used without the need for a special vacuum laminator or heating press, and even when using a normal laminator (for example, DuPont's A-24 laminator), the substrate surface does not involve air. The resist can be laminated to the surface of the substrate, and the resist can be made to adhere well to the surface of the substrate. Moreover, it is possible to provide a film photoresist that can sufficiently withstand the heat of a solder bath, has excellent resolution, and has very excellent electrical properties.

The film photoresist laminate of the present invention is a film with sufficient strength by itself, so it can be used alone, and unlike conventional film resists, it can be laminated into two layers consisting of a support film layer and a resist layer. There is no need to have a structure. The film photoresist laminate of the present invention is also suitable for laminating substrate surfaces with uneven surfaces, such as substrate surfaces with reliefs, roughened copper without relief marks, and metal plates with uneven surfaces. be. Especially in the above case, the unevenness difference is 30 μ
m or more (1) When the film photoresist laminate of the present invention and a commercially available one were laminated and their condition was observed, it was found that the film photoresist laminate of the present invention was superior because it caused significantly less air entrainment. Furthermore, when the film photoresist laminate of the present invention is used, the photomask can be brought into close contact with the resist layer during image printing, so that images with clear and high resolution can be obtained. It has sufficient heat resistance when applied to copper-plated through-hole boards, and solder-plated through-hole boards.With commercially available acrylate solder resists, soldering at 260C can be applied once to the -b'- limit (approximately 5 seconds). ), but the film photoresist laminate of the present invention changes to a resist film even when soldered at 290C for 3 minutes.
Currently, commercially available solder resists have very poor heat resistance and there are no products with satisfactory water resistance, especially on solder-plated through-hole substrates, but the film photoresist of the present invention A laminate has an extremely excellent feature of sufficient heat resistance even when the film thickness is reduced.

Moreover, the film photoresist laminate of the present invention has a thickness of 14 m
There is no peeling between the resist and the upper resist, and there is no stickiness at room temperature, so it can be handled with the support removed, and it can be exposed in close contact with the negative film, so it can overcome the low resolution of commercially available film resists. , which has the advantage of being able to print faithful patterns on negative film.

Furthermore, even printed wiring boards with unevenness of 150 μm can be laminated with a normal laminator without using a vacuum laminator, and there is no defect in adhesion to the substrate due to air entrainment.

Note that the developer for the film photoresist laminate of the present invention is not particularly limited, and for example, halogenated hydrocarbons such as 1,1.1-trichloroethane and 1,1.1-trichloroethylene can be used as the developer. can be used.

The film photoresist laminate of the present invention is a solder resist with extremely excellent heat resistance, so it is a new product that will contribute to the electronic industry and other industrial fields that require microfabrication.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Cis-1,4-polybutadiene with a weight average molecular weight of 58,000 was cyclized using a catalyst consisting of trichloroacetic acid and diethylaluminium sesquichloride in a toluene solvent, and the cyclization rate was 53%, [η]υL= = o, 43417
A cyclized product of 'g was obtained. Note that the above cyclization rate is a value determined by the following formula.

*: Measured by NMR and then toluene with a concentration of the above cyclized product of 30% by weight? g liquid xo
In the OP, phthalocyanine IJ-n (C, 1,741
60) 0.39.2-methylanthraquinone 0.6-di, 4,4'-thiobis(6-t-butyl-m-cresol) o,39, and coumaron-indene resin (NG -4) 1.5 g was added and a uniform composition was prepared using a ball mill. This composition was applied to a polyester film [DYNASHEET-38E-0 manufactured by Fujimori Industries Co., Ltd.].
0IC) and dried at 80C for 30 minutes to obtain a lower layer resist with a thickness of 15 μm.

Next, to 100 g of a 40% by weight solution of methyl methacrylate with a weight average molecular weight of 210,000 in methyl ethyl ketone, 209 trimethylolmethane triacrylate, 4 g of tributylamine, and 1.2 g of 2-methylanthraquinone were added.
9 and 2,2-methylenebis(4-methyl-6-t-
A homogeneous composition was prepared by adding 0.4 g of butylphenol) onto the lower resist layer, and the mixture was heated to 80C for 30 minutes.
After drying for 30 minutes, a film photoresist laminate having a total thickness of 56 μm was obtained.

After peeling off this film photoresist laminate from the support film, a line width of 150 μm that had been preheated to 110C was placed so that the lower layer resist was in contact with the object to be laminated.
It was laminated onto a solder-plated through-hole substrate with a line spacing of 100 μm and a relief height of 100 μm. First, in order to remove the resist in the through-hole area, the minimum land size is 50.
A μm test pattern photomask was applied closely, and a Phoenix 3000 double-sided printing machine manufactured by Oak Seisakusho Co., Ltd. was used.
After exposure for 20 seconds at a light intensity of 3000 W/m2, 1,
1.1-) When developed with lychloroethane, a clear colored image with no bleeding in the through hole area was obtained.

Next, when heat treatment was performed at 150 t:' for 60 minutes, a permanent image protective film with excellent dimensional accuracy faithful to the negative mask was obtained. After improving the adhesion of solder to metal parts by treating the surface of the board with this permanent protective film with rosin (Francs BF-1230 manufactured by Sunf Chemical Industry Co., Ltd.),
Even after being immersed in a 90 tl solder bath nine times for 20 seconds each, no change occurred, and it could be used satisfactorily as a solder resist.

In addition, in order to investigate the adhesion between the upper resist layer and the lower resist layer of the heat-resistant film photoresist laminate, various methods were used to peel them off, but no layer image of delamination was observed, indicating that the adhesion between the layers was sufficient. , even when laminating on solid surfaces,
It turned out that there were no problems.

Comparative Example 1 A laminate was manufactured under the same conditions as in Example 1 except that the coumaron-indene resin was removed, and laminated onto a solder-plated through-hole substrate, and the solder heat resistance and adhesion between the upper layer resist and the lower layer resist were examined. Ta. As a result, the adhesion between the upper layer resist and the lower layer resist is somewhat weak, and if lamination is performed without peeling off the protective film, delamination may occur between the upper layer resist and the lower layer resist in some parts1. Lifting occurred on the resist surface, and small damage was observed in that area.

Examples 2 to 5 Table 1 was used instead of the chroman-indene resin of Example 1.
The solder heat resistance of the film photoresist laminate obtained in the same manner as in Example 1, except that the tackifier was used, and the adhesion between the upper layer resist and the lower layer resist were examined.
The results were good as in Example 1.

The results are shown in Table-1.

Example 6 A lower resist was obtained in the same manner as in Example 1 except that the coumaron-indene resin in Example 1 was removed.

Next, to 100 g of a 40 weight solution of polymethyl methacrylate having a molecular weight of 210,000 in methyl ethyl ketone, 209 g of trimethylolmethane triacrylate, 29.2 g of tributylamine, and 1.29.2 g of 1,2-benzanthraquinone.
．． Add 0.49 of 2-methylenebis(4-methyl-6-t-butylphenol) and 1.59 of aromatic petroleum resin (1 Trozine "#" 80) manufactured by Mitsui Petrochemicals Co., Ltd.
A uniform composition was coated on the lower resist layer and dried at 80C for 30 minutes to obtain a film photoresist laminate with a total thickness of 66 μm.

After this film photoresist laminate was peeled off from the support film, a line width of 150 μm1, which had been preheated to 1xoc, was placed so that the lower layer resist was in contact with the object to be laminated.
Line spacing is 100μm.

It was laminated onto a solder-plated through-hole substrate with a height of 100 μm. Next, in order to remove the resist in the through-hole area, a test pattern photomask with a minimum land of 50 μm was closely attached, and a new Phoenix 3000 double-sided printing machine manufactured by Oak Seisaku Co., Ltd. was used with a light intensity of 3000 W/m.
2 for 20 seconds, and then developed with 1,1,1-trichloroethane, a clear colored image with no bleeding in the throughhole areas was obtained.

Next, heat treatment was performed at 150 C for 60 minutes, and a permanent image protective film with excellent dimensional accuracy faithful to the negative mask was obtained. This permanent protective film is coated with Sunf Chemical Industry Flux 5F.
- After processing with 1230, go to 2901Z” solder bath 2
No change was observed even after 9 times of immersion for 0 seconds each, and the resist was sufficiently usable as a primer resist.

In addition, in order to investigate the adhesion between the upper resist layer and the lower resist layer of the heat-resistant film photoresist laminate, we tried peeling them using various methods, but no delamination phenomenon was observed, and the adhesion between the layers was sufficient. Even when laminating on solid surfaces,
It turned out that there were no problems.

Claims (1)

[Claims] (A) a lower resist consisting of a composition containing a cyclized product of a butadiene polymer as an essential component, and (B), (a) a polymer or copolymer of a monoolefinic unsaturated compound 100
Parts by weight, (b) polyfunctional photopolymerizable unsaturated compound having at least two or more photopolymerizable double bonds in the molecule 5 to 100
parts by weight, (C) Photostripe A lower layer resist of a film photoresist laminate and/or an upper layer resist consisting of a composition containing at least 1 m of a photoresist selected from a bridging agent, a photosensitizer, and a photopolymerization initiator. A tackifier is added to the upper resist as a cyclized product of a butadiene polymer or a polymer or copolymer of a monoolefinic unsaturated compound.
Blend at a ratio of 0.1 to 50 parts by weight to parts by weight
A heat-resistant film photoresist laminate characterized by: