JPS6177844A - Novel photopolymerizable laminate - Google Patents

Abstract

PURPOSE:To obtain an extremely precise printed circuit superior in mechanical strength and plating resistance by forming a photopolymerizable laminate composed of a specified polymerizable layer and a support and exposing it to light. CONSTITUTION:The printed circuit high in density and precision can be obtained by forming a photopolymerizable laminate composed of 5-95wt% binder made of a vinyl (co)polymer, 0.01-30wt% photopolymerization initiator, and 95-5wt% photopolymerizable unsatd. compd. essentially composed of one of photopolymer izable compds. having a mol.wt./number of contained double bonds ratio of <=1,000 represented by general formulae A, B or C in which n is an integer of >=0; m is an integer of 3-10; R1 is H or methyl; X is a 1-8C divalent aliphat ic group or the like; R2 is 1-6C alkyl or CH2-O-R4; R4 is phenyl, aryl, or 1-6C alkyl; Y is a 2-16C divalent hydrocarbon group; and Z is -(CH2)t-O.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to novel photopolymerizable laminates, and more particularly to photopolymerizable laminates suitable for making printed circuit boards.

(Prior Art) Conventionally, so-called dry film resists (composed of a support layer and a photopolymerizable layer) have been used as resists for producing printed circuit boards.
(hereinafter referred to as DFR) is used. DFR is
It is generally prepared by laminating a photopolymerizable composition on a support film and, in many cases, further laminating a protective film on the composition. To make a printed circuit board using DFR'i, the protective film is peeled off, the KDFR'i is laminated on a permanent image forming substrate such as a copper clad laminate, and the whole is exposed to light through a mask film or the like. Next, the support film is peeled off if necessary, and the photopolymerizable composition in the red exposed area is completely dissolved or dispersed in a developer to form a cured resist image on the substrate.

Hereinafter, the process of forming a circuit can be roughly divided into two methods. The first method is to remove the copper surface that is not covered by the hardened resist by etching, and then further remove the resist.The second method is to perform plating treatment such as solder on the same copper surface, and then , the resist is removed, and the exposed steel surface is etched.

Recently, in printed circuit boards exploded using DFR'i,
Increasingly, one side of a permanent imaging substrate is electrically connected to the other by a conductive circuit-forming material layer, such as a copper thin film layer, attached to the inner circumferential surface of the through-hole. . The copper through-hole method and the solder through-hole method are common methods for manufacturing this type of printed circuit board, and among the copper through-hole methods, the tenting method is becoming widely adopted. . This tenting method involves simultaneous exposure and curing and formation of a nine-wire image.

When etching a thin copper film or the like to form wiring by completely closing both openings of the through hole with a photocured layer, it is necessary to ensure that the photocured layer protects the conductive layer on the inner peripheral surface of the through hole. , it is possible to obtain a printed circuit in which both surfaces are electrically connected through the null-hole.

The conductive circuit forming material layer on the inner circumferential surface of the through hole is limited in specific gravity due to circuit design constraints. Therefore, in the tenting method, the exposed photopolymerizable layer that closes the openings on both sides of the through hole in a tent-like manner is supported by a band-shaped portion having an extremely narrow width. The photopolymerizable layer supported in a tent-like manner and exposed to light is frequently exposed to light during development and etching by being showered with respective processing solutions, resulting in damage to the photopolymerizable layer and damage to the permanent image forming substrate. The photopolymerizable layer of DFH used in the tenting method is required to have mechanical strength after exposure, adhesion to the permanent image forming substrate, and chemical resistance. Ru.

By the way, the photopolymerizable layer of DFH that is currently widely used consists of +1) an unsaturated compound (hereinafter referred to as a monomer) having at least one ethylenic group and capable of forming a polymer with a photopolymerization initiator; (2) Thermoplastic organic polymer binder (hereinafter referred to as binder), (31) consisting of a photopolymerization initiator and (A) other additives (
I# Publication No. 50-9177, Special Publication No. 57-2169
Publication No. 7).

Examples of the monomer include trimethylolpropane triacrylate and pentaerythritol triacrylate having two or more ethylenic double bonds, and polyethylene glycol diacrylate having an ether bond in the molecular chain. There is. on the other hand,
As the binder, a binder is selected that is compatible with the monomer, such as polymethyl methacrylate, methacrylic ester, acrylic ester, and copolymers of acrylic acid, methacrylic acid, styrene, and the like.

However, the mechanical strength of the exposed photopolymerizable layer and its adhesion to the substrate are affected by the type and amount ratio of the monomers and binders used, and the influence of the monomers is particularly large. Mechanical strength, chemical resistance, and adhesion with the substrate after exposure of the polymerizable layer are not necessarily sufficient if the photopolymerizable layer is thin, and especially when used in the tenting method, the photopolymerizable layer must be thick. There is a need to.

On the other hand, the demand for electronic components and elements to be made more compact (by packaging them and making the entire product smaller) is becoming stronger and stronger. It is being

This method of forming a high-density printed circuit requires that the DFH used has high resolution, but the thicker the photopolymerizable layer, the lower the resolution. Therefore, when forming an image using the DFRt-tenting method comprising a photopolymerizable layer as described above, it is difficult to obtain an extremely precise and high-density circuit image.

On the other hand, the solder through-hole method, which is still widely used to form printed circuits, uses an etching-resistant metal, such as solder, to protect the conductive circuit material layer, such as a copper thin film layer, on the inner circumferential surface of the through-hole. The process involves resisting and then etching away unwanted areas on the surface of the permanent imaging substrate. In this solder through-hole method, the image-formed substrate covered with a hardened resist layer is first subjected to various treatments such as degreasing by alkaline cleaning, degreasing by surfactant aqueous solution cleaning, and electrolytic polishing. It undergoes electroless copper plating, then copper plating and solder plating.

In high-density printed circuit boards, the circuit gaps are naturally designed to be narrow, so during plating pre-treatment and plating, processing and plating solutions may seep into the resist and between the resist and the board, and small floats in the resist. became a big problem,
Therefore, a DFR with excellent pretreatment chemical resistance, copper plating resistance, and solder plating resistance is required. −Secondary,
The copper plating resistance, solder plating resistance, and pretreatment chemical resistance of the exposed photopolymerizable layer are also influenced by the type of monomer and binder in the photopolymerizable layer, and the type and amount of monomer are particularly important. influence. As monomers, ester bonds such as trimethylolpropane triacrylate and polyethylene glycol diacrylate shown above are used. The photopolymerizable layer has particularly poor copper plating resistance, solder plating resistance, and pretreatment chemical resistance.

Ninth, as an improved method for making printed circuit boards using DFR, using DFRi, the support layer consists of a film that is dissolved or dispersed in the developer of the photopolymerizable layer, and development can be performed without peeling off the support film after exposure. A method is known in which these substances are removed at the same time through treatment (Japanese Patent Application Laid-Open No. 113752/1983). This method has major advantages such as being able to avoid partial destruction of the image that can occur when the support film is completely mechanically peeled off, shortening the process by 7 tons, and enabling continuous automatic processing. .

(Problems to be Solved by the Invention) As mentioned above, acrylic esters or methacrylic esters having only ester bonds or ester bonds and ether bonds, such as trimethylolprobandoliacrylate and polyethylene glycol diacrylate, The secondary photopolymerizable layer has insufficient copper plating resistance, solder plating resistance, and processing chemical resistance. And the improved method of making the printed circuit board Ki? Even if
If the above-mentioned monomer is used as the monomer in the photopolymerizable layer and the DFR is laminated to the substrate at an excessively high temperature and under strong tension, fine cracks may occur in the laminated support film of the 90FR. I don't like it when it occurs.

(Means for solving the problem) Based on the above background, both the copper through-hole method and the solder through-hole method, which have good mechanical strength after exposure and excellent plating resistance, are extremely effective. As a result of our efforts to develop a photopolymerizable laminate that enables the production of precision printed circuit boards, we have discovered the laminate of the present invention.The present invention consists of a photopolymerizable layer and a support layer. If necessary, a protective layer d (in the existing photopolymerizable laminate, the photopolymerizable layer and (1) vinyl polymer or vinyl copolymer) may be added to the other surface of the photopolymerizable layer. Goo 5-9
5% by weight (2) The following general formula (A) or (B)'! Taha (C
) A photopolymerizable unsaturated compound whose main component is a photopolymerizable compound whose molecular weight/number of double bonds contained is 1000 or less 95 to 5 weight - (3) Photopolymerization initiator 0.01 to 30% by weight of the photopolymerizable laminate.

(C) [where n is an integer of 0 or more, mFis or an integer of 10, Rs is hydrogen or a methyl group, or a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or 17'c is (wherein %R3
is an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 10, ql' is an integer of 1 to 4, respectively), R3 is an alkyl group having 1 to 6 carbon atoms, and C) I, -0-R
4 (R is a phenyl group, an allyl group, an alkyl group having 1 to 6 carbon atoms), Y is a divalent hydrocarbon group having 2 to 16 carbon atoms, 2 is an integer from Rs to 10, and X is 1 to 3. (an integer of 0), (wherein is a trivalent hydrocarbon group having 3 to 10 carbon atoms, and S is 1
(an integer from 5 to 5). ] Next, the laminate of the present invention will be explained in detail.

As the binder, a thermoplastic polymer consisting of a polymer or copolymer of vinyl monomers is used, among which a heptad polymer represented by the following structural formula (b),
Or a copolymer consisting of them is preferred.

[In the formula, vl is hydrogen, 9 is a methyl group, ■ is phenyl,
C1-C10 alkyl group, vinyl group) represented by t-. ] More preferably, a polymer or copolymer of methyl methacrylate, methyl acrylate, butyl acrylate, styrene, butadiene, etc., which has good solubility in alpha-genated hydrocarbons, is more preferable.

The molecular weight of the binder is 20.000 in weight average molecular weight.
Preferably, K is 500,000 to 500,000, and K is s
o, o o o 1. nl, 300. O of OOQ is preferable. If the molecular weight is too large, the development time will be long, which is undesirable. (9) If the molecular weight is too small, the mechanical strength of the cured resist will decrease, which is not preferable.

It is necessary that the value obtained by dividing the molecular weight of Fi as a monomer by the number of double bonds contained is 1000 or less, and preferably 100 or more and 700 or less.

In the above-mentioned structural formula (A), the ω) formula is selected from those shown in C), but it is also possible to combine a plurality of seven formulas.

Regarding structural formula (g)K, the upper limit of n is determined by the molecular weight of the above-mentioned monomer (equivalent to the double bond). R
1 is hydrogen and is a methyl group, but hydrogen is more preferable from the point of polymerizability. R3 is preferably an alkyl group having 1 to 4 carbon atoms, - is preferably a methyl group or an ethyl group, and l/ and @y are preferably selected from the following group.

(However, U represents all integers from 4 to 8.) Among these, hexamethylene group and tolylene group are more preferred.

2, the ratio of ÷cH inaso- is (-CHI-(j'
H-0+x is preferable, where t is an integer of 2 to 10 and X is an integer of 1 to 3o, but the values of t and xO are also limited by limitations on the molecular weight of the monomer. As R1, methyl is preferred here.

In the structural formula), the following structural formulas g1 to E4 are used.
Those shown are preferred.

(Here, wf...represents a trivalent hydrocarbon group of Rengeki 3 to 1o, mFi an integer of 5 to 10. Among these, those where Wl is a structural formula (龜) and Y is a hexamethylev group,
Preferably, crane is represented by the following structural formula (E,), and Y is hexamethylene and te is tolylene group.

Among Structural Formulas (A), ω), and (C), monomers represented by Structural Formula (A) are preferred, and a mixture of those in which n is O to 2 to 31 is preferred.

Next, one example of a method for producing these monomers will be briefly described.

Among the monomers represented by the structural formula (F), n=00 can be obtained by reacting a raw material monomer represented by the structural formula (F,) below with a diisocyanate represented by the structural formula (F,). It will be done.

0CN-Y-NCO(F, ) Here, when a diol represented by the following structural formula (F,) is further coexisted, a heptadium represented by the structural formula (A) where n is 1 or more is generated. , at this time, n=00 is also generated simultaneously.

HOZ=H(FA) Further, the monomer represented by the structural formula (B) has the structural formula (F
It is a reaction product of a monomer represented by l) and a polyisocyanate represented by the following structural formula (F,), W(-NCO) (F4), where it is represented by the structural formula (Fl). When a diol is present, a monomer represented by structural formula (C) is also produced. When diol (Fs) is used as a raw material, first, diol (F,) and incyanate are reacted to form incyanate oligo-r-f, and then monomer (
r+) is preferably added.

Preferred specific examples of the monomer (Fl) include 2-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxy acrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, acryloxy Examples include ethyl-2-hydroxypropyl-phthalate and methacryloxyethyl-2-hydroxypropyl-phthalate.

Preferred examples of diisocyanate (p,) include hexamethylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, inphorone diisocyanate, 2,2.5 -) Limethylhexamethylene diisocyanate, etc.

Representative examples of diols (Fl) include ethylene glycol, propylene glycol, methanediol, hexanediol, and diols represented by the following structural formula (Fs).

Here, R1 is hydrogen or methyl, and zl is +C
H! -)tO-1+CH, -C'H-0+x are preferred.

(wherein, t and There is an adduct. The reaction is preferably carried out in a solvent, and aromatic hydrocarbons such as toluene and xylene,
Preferred are esters such as ethyl acetate and butyl propionate, and ketones such as acetone, methyl ethyl ketone, and methyl ibutyl ketone.

Although the reaction can be carried out either in the absence of a catalyst or in the presence of a catalyst, it is preferable to use a catalyst to speed up the reaction. Examples of catalysts used include tertiary amines such as evatriethylamine and triethylene diamine, and tin compounds such as stannath octoate and dibutyltin dilaurate.

It is desirable that the reaction be carried out under conditions in which the carbon-carbon double bonds of compounds (F, ) and (Fs) do not polymerize, and for this purpose the reaction temperature is below FiaoC, preferably below 50C. Further, it is desirable to conduct the reaction while blocking active light.

Further, it is preferable that the reaction is carried out using 1 equivalent or more of active hydrogen group per equivalent of isocyanate group to eliminate free incyanato groups.10 As is clear from structural formulas (A) to (C), the present invention The so-called urethane (meth)acrylate disclosed in
It is essential that it is a t-type urethane compound produced from isocyanate 7-secondary alcohol.

For example, JP-A-47-13912, JP-A No. 50-92124
, No. 54-153624, etc., in which R is hydrogen, a developer commonly used during image formation by DFR, such as 1, 1, 1-
) Not significantly soluble in dichloroethane, trichlorethylene, etc., or methylene chloride, which is a stripper of hardened resist.
＜Not only does it have the problem that even if the uncured resist or cured resist is peeled off, a small amount of monomer remains on the substrate, and subsequent processes such as plating and etching do not proceed uniformly or completely. They often have poor compatibility with the photopolymerizable layer, and whitening of the photopolymerizable layer is also observed, making them undesirable for photoresists that require transparency throughout their life.

Other photopolymerizable compounds can be added to the photopolymerizable layer of the present invention, preferably in amounts that do not constitute the main component.

As the photopolymerizable compound, formula (F・) or F+
s).

In the formula, z is hydrogen, methyl and halogen, and z.

is phenyl, vinylphenyl, cyano, halogen, pyridyl, imidazolyl or -C-O-Z4 (where z
4 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an allyl group, a benzyl group, a hydroxyalkyl group having 2 to 6 carbon atoms, or a hydroxyalkyl group having 3 to 8 carbon atoms;
dialkylaminoalkyl group, C1-C6 haloalkyl group, tetrahydrofurfuryl group, halophenyl group, carpitol group (wherein nine is hydrogen), such as styrene, divinylbenzene, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile , and ethyl acrylate, inglovir acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, carpitol acrylate, methoxyethylene glycol acrylate, dimethylaminoethyl acrylate, acrylic acid Acrylic esters such as diethylaminoethyl, tetrahydrofurfuryl acrylate, 2-chloroethyl acrylate, 2,3-dibromoprobyl acrylate, tribromophenyl acrylate, allyl acrylate, or corresponding methacrylic esters1. These include vinylpyridine and vinylimidazole.

In the formula, z is a divalent alkyl having 2 to 1 carbon atoms, and t is 1
Or 20! number, R6 is hydrogen or methyl),
Examples of monomers (F,) include diacrylates and dimethacrylates of diols such as bentanediol, hexa/diol, ethylene glycol, tetraethylene glycol, nonaethylene glycol, polyethylene glycol, neobentanediol, polypropylene glycol.

In the formula, z6 is a trivalent alkyl group having 3 to 12 carbon atoms,
trivalent flukoxyalkyl group having 6 to 14 carbon atoms or υ, bird as previously defined;

Examples of monomers (F8) include trimethylolpropane triacrylate, tri(acryloxypropoxy)
Hexane, tri(acryloxypropoxy)prop/,
tri(hydroxyethyl)triazine acrylate and the corresponding methacrylic acid ester.

During the ceremony, Z? From zl! At least 3 of them are hydroxy groups, and i is 0 and i is 1.

Examples of nanatsumer (F) include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate,
Examples include dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, and dipentaerythritol triacrylate.

In the formula, %zts is a divalent alkyl group having 1 to 8 carbon atoms, and examples thereof include "Mw Aronix" manufactured by Toagosei Chemical Industry Co., Ltd.

In the formula, z14 is an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms.

Examples of the monomer (Fu) include acrylamide, methylenebisacrylamide, Nt-butylacrylamide, Nt-octylacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide,
and the corresponding methacrylamide.

In the formula, R1 is hydrogen and 9 are methyl.

In the formula, zts is hydrogen, t7t is an alkyl group having 1 to 10 carbon atoms, and examples of the monomer (Frs) include silicon and acid, ethyl cinnamate, and propyl silicon and acid.

:1 In the formula, 21. is hydrogen, and phenyl is hydrogen (FI4).
4) In the formula, s R1+zl is already defined.

(Fu) R and water are methyl, and n is an integer from 1 to 4.

Examples of the photopolymerization initiator or photosensitizer that can be used in the present invention include benzoin, benzoin alkyl ether,
Polynuclear quinones such as anthraquinone, benzophenone,
Chlorbenzopheno/, Michler Ketone, Freonone,
thiosanthone, dialkylthioxanthone, halogenated thioxanthone, isoamyl dimethylaminobenzoate, dimethethyl benzoate, naphthalenesulfonyl chloride-azobisisobutyronitrile, 1-7zobis-1-cyclohexanecarboni),! J”, 2e’
-dichlorobenzoyl peroxide, diphenyl disulfide, dipenzothiazole, 1-(A-inglobylphenyl)-2-hydroxy-2-methylpropane-1
-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one; dyes and electron-donating substances such as erythrosine, triethylamine, p-aminobenzoic acid esters, triphenylphosphine, 2-2-dimethoxy-2
-722-acetophenol and the like. These photopolymerization initiators or photosensitizers may be used alone or in combination of two or more. is 5 to 95, preferably #i20 to 8
0%, more preferably 30 to 70%. The total monomer content is 95 to 5%, preferably 80 to 20%, more preferably 70 to 50%.

Furthermore, the monomer having the highest content of 91 among these monomers must be a monomer represented by the structural formula (A), and (n)kt must be a monomer represented by (C). The content of photoinitiator is 0.01
from 0.1 to 50 inches, preferably from 0.1 to 15 inches,
More preferably, it is 1 to 10 inches.

Furthermore, the photopolymerizable layer of the present invention may optionally contain a dye,
Additives such as stabilizers, copper surface adhesives, plasticizers, etc. can also be added.

The thickness of the photopolymerizable layer varies depending on the application, but for printed circuit board production (5 to 150 μm, preferably 5 to 70 μm); the thinner the layer, the better the resolution.

The support layer used in the photopolymerizable laminate of the present invention may be transparent or completely opaque to actinic light, but it may be difficult to perform the image forming process and prevent dust from adhering during exposure. Taking this into consideration, a transparent material that transmits active light is desirable.

As the support layer that transmits active light, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, hinyl chloride copolymer film,
Polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate film, methyl methacrylate copolymer film, polystyrene film,
Examples include polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film.

As already mentioned, the method of forming a resist image by developing and removing the unexposed parts of the support layer and the photopolymerizable layer without peeling the support layer from the photopolymerizable layer simplifies the process. However, if the photopolymerizable layer of the present invention is applied, it can be used under severe lamination conditions without causing cracks in the book or support film. In this case, the support needs to be a material that can dissolve or disperse the photopolymerizable metal.

As the support, when the developing liquid is an organic solvent, polymethyl methacrylate film, methyl methacrylate copolymer film, polystyrene film, styrene copolymer film, etc. are particularly preferred from the viewpoint of solubility; When the liquid is aqueous, amino groups, ammonium groups,
Preferred are polymer films containing hydroxyl groups, carboxyl groups, and salts thereof, such as polyvinyl alcohol films, cellulose derivatives, and the like.

Although the storage layer is not an essential constituent, it must be easy to peel off from the photopolymerizable layer, and it is preferably made of polyethylene film, polypropylene film, cellophane, polyethylene terephthalate treated with a release agent, release paper, etc. be.

The photopolymerizable layer of the present invention is cured by irradiation with active light, and the active light here refers to visible light, ultraviolet rays, and electron beams, and light sources include the sun, arc lamps, mercury lamps, high-pressure mercury lamps, and ultraviolet rays. There are high-pressure mercury lamps, germicidal lamps, xenon lamps, fluorescent lamps, etc.

(Effects of the Invention) The photopolymerized laminate of the present invention is particularly useful for forming printed circuit boards. A printed wiring board can be produced with extremely good results using a photopolymerized laminate by a conventionally known method.

In the tenting method, high mechanical strength of the cured film,
Reflecting the adhesion to the substrate, there is significantly less damage to the through-hole closing film during development or etching. Maku,
In the solder through-hole method, good plating resistance was exhibited without penetrating the interface KB between the resist and the substrate, such as a plating solution, during plating. Further, since the uncured photopolymerizable layer can be completely removed by development, etching and plating can be performed extremely uniformly. Furthermore, the present photopolymerizable layer has high photosensitivity and shortens exposure time.

That is, by using the photopolymerizable laminate of the present invention, it is easy to produce a printed circuit board with high density and high precision, and furthermore, there is an advantage that the printed circuit board exploding process can be simplified.

Furthermore, the photopolymerizable laminate of the present invention can be used as a solder resist film, and can also be applied to the production of decorative boards and printing plates, and the etching process of nameplates, pattern boards, etc.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Reference Example 1 In a 92-volume four-bottle flask equipped with a dropping funnel, a thermometer, and a stirrer, 148 % of hexamethylene diisocyaner (P) was added as the compound (F), and 80 % of dry methyl ethyl ketone was used as the solvent 1. , and dibutyltin dilauret as a catalyst), and while stirring, add the compound (
A mixture of 286f 2-hydroxypropyl acrylate (F+) and 651 methyl ethyl ketone (solvent 2) was added dropwise so that the internal temperature did not exceed 55Cf. After the dropwise addition, stirring was continued for 50 hours at 40C, and it was confirmed that the characteristic absorption of the incyanate group near 2270crII-1 almost disappeared in the infrared absorption spectrum. Next solvent 3
50? Next, add methyl ethyl ketone. This reaction product is referred to as 1c-1.

Reference Example 2 In the same flask as Reference Example 1, add 5say of (2,4-)lylene diisocyanate, 80t of acetone, and 0.649f of dibutyltin dilaurate, and stir.
Drop a mixed solution of hydroxypropyl acrylate 3362 and 215f in acetone and continue stirring for 25 hours. During this time, adjust the internal temperature so that it does not exceed 40C. A portion of the reaction mixture was sampled, an equal amount of ethanol was added, the mixture was left at 50C for 1 hour, and the sample was analyzed by gel permeation chromatography. No adduct of tolylene diisocyanate and ethanol was observed. ,
It was confirmed that tolylene diinocyanate was consumed in the reaction. This reaction mixture is designated as C-2.

Reference Example 3 In an 11-volume Mitsuro flask, propylene glycol diglycidyl ether diacrylate (Nagase Sangyo Co., Ltd. Hidenacol Acrylate) DA-911: hydroxyl equivalent 22
2) 97,7 r and the above C-2213011 dibutyltin dilaure) 0.3? , add acetone 751,
4 hours at 30C with magnetic stirring, then 12 hours at 45C.
Continue the reaction for some time and confirm the completion of the reaction by infrared absorption spectrum. This product is designated as t-C-3.

Reference Example 4 In the Yotsuro flask used in Reference Example 1, compound (F) was added as solvent 1 and 200% ether was added as compound (F,). Polyethylene glycol (with an average molecular weight of 200) was added dropwise over a total of 2 hours. During this time, the temperature of the water bath and the dropping rate are fully adjusted.
The temperature was adjusted so that the internal temperature did not exceed 40 Ct. After further stirring at 40C for 1 hour, compound (F, ) was obtained as 2-hydroxypropyl acrylate 1549! f, internal temperature 40C
1 - Dropped so as not to exceed. After that, after stirring at 40C for 48 hours, 100℃ was used as solvent 2. Add ethyl acetate to make a homogeneous solution. This is designated as C-4.

Reference Examples 5 to 13 Table 1 shows the types and amounts of raw materials that were prepared using the same apparatus and method as in Reference Example 1 to prepare a seven-layer [reactant (, C)]. In all cases, dibutyltin dilaurate was used as the catalyst. 9. Let the products on each side be C-4 to C-15, respectively.

Notes to Table 1 *1) IPDI; influoron diincyanate *2)
HPA; 2-hydroxyglobyl acrylate *3
) DNT: HMDI adduct (Duranate 24A-100 manufactured by Asahi Kasei Corporation) *4) MEK: Methyl ethyl ketone *5) B-,1
; 2-Hydroxy-5-phenoxypropyl acrylate [Aroex (AR) manufactured by Toagosei Chemical Industry Co., Ltd.
ONIX) 5700) *6) HMDI; Hexamethylene diisocyanate *7) CHL: HMDI trimethylolpropane adduct (Coronate HL manufactured by Nippon Polyurethane Industries Co., Ltd., NGO content 12.8%.

75% ethyl acetate solution) *13) CL;) Lylene diincyanate trimethylolpropane adduct (Coronate L manufactured by Nippon Polyurethane Industries Co., Ltd., NGO content 13.2%, 75%
Ethyl acetate solution) 9) B-2; Polypropylene glycol monomethacrylate (NOF Premer p-1000° average molecular weight 370) *10) TDI:) lylene diisocyanate *11
) MDI Nidiphenylmethane diisocyanate *1
2) TMHMDI: ) Limethylhexamethylene diinocyanate Reference Example 14 DNT as compound (6) (Table 1 *3) 96
f.

As solvent 1, 80t of methyl ethyl ketone, compound (Fs
), 20f polyethylene glycol (average molecular weight 200), compound (F, ), 2-hydroxypropyl acrylate, 52t, solvent 2, 52t methyl ethyl ketone, and reference example 4 except that a separable flask with a capacity of 1 was used as the reaction vessel. The product C is reacted in the same manner as
-14 was obtained.

Reference Example 15 Put 2000F of ion-exchanged water into a 5-inch capacity mono-rubber flask equipped with a stirrer and a reflux condenser, and add 10p of methyl cellulose (Metrose 5H-100 manufactured by Shin-Etsu Chemical).
, dissolve 5f of sodium chloride and stir at 75C to form methyl methacrylate as a monomer. and butyl acrylate 20f1 azobisin butyronitrile 2.5
f. A homogeneous mixture of 12 dodecyl mercaptans was charged.

After about an hour, the internal temperature began to rise and reached 90 Ct. 8
When the internal temperature dropped to 0C, the water bath was raised to 800C for 2 hours, then stirred at 90C for 1 hour.
It was poured into a 0.00 mesh gold plate and washed with a sufficient amount of water. As a result, bead-shaped polymers with a particle size of 100 to 400 microns were obtained and dried. 8-15 of this polymer
And fru.

When this B-15 was analyzed by gel permeation chromatography, it was found to have a weight average molecular weight of 176.000.

Example 1 B-15499 as a binder and C- as a monomer were placed in a 30-row separable flask equipped with a stirrer.
1557, benzophenone 2f and Michler's ketone 0.2f as initiators, and Diaresin Blue P (as dye).
(manufactured by Mitsubishi Chemical Industries, Ltd.), benzotriazole 0.2 as an additive. , I)-Meth'oxyphenol 50mg
, Ethyl acetate 842 was added as a solvent, and the mixture was stirred for 15 hours.

Next, the mixture was applied onto a 20μ polyethylene terephthalate film as a support layer using a blade coater, air-dried for 50 minutes, and then dried in the open at 60C for 15 minutes. Thickness Fi3 of the obtained photopolymerizable layer
It was 5μ. Next, this photosensitive layer is coated with 25% as a protective layer.
After laminating a μ polyethylene film using a pressure roll, the polyethylene film was peeled off and pressed onto a copper-clad glass epoxy laminate using an 80C pressure roll. This laminate was exposed to light through a negative mask film using an ultra-high pressure mercury lamp (Oak Seisakusho Phoenix 3000 model) at a dose of 100 mJ per 1 c++f. Next, the polyethylene terephthalate film was peeled off and 1,1,1-tricumylethane was applied for 120 seconds using a spray nozzle to dissolve and remove the unexposed areas, resulting in a good image (this is referred to as a resist image).
I got it. It was confirmed that it exhibited a dissolving power of 40μ. Next 5
A 0C ferric chloride solution was sprayed for 2 minutes to etch the exposed copper surface, but no image bleeding was observed.

, Example 2 In a 10 t separable flask equipped with a stirrer and a reflux condenser, 1960 f of methacrylic resin (Delpetsu, manufactured by Asahi Kasei Corporation) 1960 f as a binder and methyl ethyl ketone 50001 as a solvent were stirred and dissolved at 70 C. Later, as a monomer, C-41880
? and dipentaerythritol pentaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) 352f, benzophenone 802 and Michler's ketone 81 as initiators, Diaresin blue P20f and benzotriazole 81 as dyes.
, 1.31 p-methoxyphenol was added, stirred for 6 hours, and then this solution was coated on a 20μ polyethylene film as a protective layer using a coating machine, and the solvent was dried to form a 40μ thick layer. After forming a photosensitive layer, the laminate was wound into a roll while being covered with a 15 μm stretched polystyrene film serving as a support. This laminate is called L-2. Next, using two of these roll-shaped laminates and using a printed circuit board laminator, a through-hole board (A, with 10 holes of 0 diameter at intervals of 4.01t1) was used.
A laminate substrate was obtained by adhesively laminating a photosensitive layer supported by polystyrene while peeling off a polyethylene film on both sides of a copper-plated glass epoxy substrate with 64 holes (the through-holes were also copper-plated). At this time, the heating roll of the laminator was set to 80CK. This laminated board was heated to 120 mJ/Cr using an ultra-high pressure mercury lamp.
/I amount of irradiation, 1,1.1-)lichloroethane was sprayed for 120 seconds, a development operation was performed, and the number of breaks in the cured film on the through holes was counted, but no breaks were observed (this The test will be referred to as Tenting-I).

Next, saC ferric chloride solution was sprayed onto the developed substrate and an etching operation was performed for 2 minutes, but no tearing was observed (this test is referred to as tenting-■). Next, using another laminate substrate, it was exposed to light under the above conditions through a land mask from both sides to form a cured film with a diameter of 4.6 on both sides of each through hole, and the tenting
, A test similar to ■ was conducted. Rand I for each test.

Although land ■ was used, no holes were observed in either case.

Example 3 A photosensitive composition was prepared in the same manner as in Example 1 except that no dye was used, and a 120μ photosensitive layer was formed on a 38μ thick polyethylene terephthalate film using a coating machine. The film covered material was wound up into a roll.

While peeling off the polyethylene film, place this laminate on a plywood board using a laminator with a rubber roll and a high-pressure mercury lamp.
When the polyethylene terephthalate film was peeled off after exposure at 0.00 mJ/d, a tough coating film was formed on the plywood. The lead hardness of this film was #i4H. Further, a 500 hour exposure test was conducted using a Weather O-meter, but there was no change in appearance, surface hardness, adhesion to plywood, etc.

Examples 4 to 17 Using the same apparatus as in Example 2, dry film resist laminates were formed in the same manner. Table 2 K summarizes the raw materials and amounts used, the thickness of the resist layer, the protective layer, and the support. In addition, for 6 examples, resist solutions were prepared by adding 0.2% benzotriazole and 0.05% p-methoxyphenol based on the combined weight of monomer and binder. The obtained laminates were each L-4.
~ Referred to as L-17.

In addition, in Examples 6, 12.15, and 14.17, unlike Example 2, after forming a photosensitive layer on the support layer, a protective layer film was laminated to form a rolled laminate. I let it happen. Also, in these cases, as in Example 1, the support film was peeled off by hand before development. Furthermore, the tenting and land test MO results are shown in Table 3.

(Nanatsuma) M-1: "Aronix M-305J (main ingredient: pentaerythritol triacrylate)" manufactured by Toagosei Chemical Co., Ltd. (hereinafter referred to as Toagosei) M-2: Nippon Kayaku Co., Ltd. 1'-D-130J (Main component: dipentaerythritol triacrylate) M-5; Epoxy ester 70PAJ (Main component: Propylene glycol diglycidyl) manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd. (hereinafter referred to as Kyoeisha Yushi) ether/acrylic acid adduct) M-4; “Viscoat 3700J [Main component, Bis(1
, 5-bentanediol) phthalic anhydride-acrylic ester] M-5: Kyoeisha Yushiki [Epoxy ester B
P-4PAJM-6; Toagosei Club “Aronix a1
oOJ (polyfunctional acrylic acid ester) M-7; Osaka organic chemical table "Viscoat 825J (non-yellowing type urethane acrylate average molecular weight 135G) M-
8: 1'-R-526J (polyester type diacrylate) manufactured by Kyoeisha Yushi M-9: Toagosei Department "Aronix M-1200J (non-yellowing type urethane acrylate) M-10: rsp-4o1o manufactured by Showa Kobunshi Co., Ltd." (
Special epoxy acrylate) (binder) B-1; Asahi Kasei Corporation Delvet 8ONB-
2: Styron P685 B-5 manufactured by the same company; Acryvet B-4 manufactured by Mitsubishi Rayon Co., Ltd.
; manufactured by Asahi Kasei Corporation Delvera) CR-IB-5=
Delpet 70HB-6 manufactured by the same company = Asaflex AFX-8IQ manufactured by the same company (initiator) Knee 1; 2,4-diingrovirthioxanthone I-2
: 4-(dimethylamino)isopropyl benzoate ■-3: Penzo7dinone I-4; 4,4'-(dimethylamino)benzophenone A 5; Fluorein 1-b; Dimethylbenzyl ketal I-7; Triphenyl Phosphine I-8: 4-chlorothioxanthone ■-9: Ethyl 4-(dimethylamino)benzoate I-
10: 4-chlorobenzophenone (dye) D-1: "Blue-P" D- manufactured by Mitsubishi Chemical Corporation
2: "Green-C" manufactured by the same company D-3; "Blue-" manufactured by the same company D-4; "Blue-G" manufactured by the same company (protective layer) (Support) P Oriented polypropylene (20μ) S Oriented polystyrene (15μ )
E Polyethylene (38 μ) T Polyethylene terephthalate (20 μ) Table 3 Example 1B The photosensitive layer obtained in Example 1 was laminated and exposed to light at a dose of 100 mJ/all through a positive mask film on a nine copper clad laminate. Friends. Next, development was performed with 1,1,1-trichloroethane, and then [40C Nutraclean C (manufactured by Silapray Far East) K immersion for 3 minutes → washing with water → immersion in aqueous solution of 20% ammonium sulfate for 1 minute → washing with water →
After performing pretreatment in the order of immersion in an aqueous ammonium 20 thiosulfate solution for 2 minutes and rinsing with water, copper plating was performed with a sulfuric acid steel plating solution under the conditions noted in Table 4, and then soldering was performed under the same conditions F. Next is plating. As a result, the flow of the thin line continued (I stuck cellophane tape on the image that could not be seen), and after applying sufficient pressure and peeling off the tape, there was no peeling of the resist at all. Further, another substrate subjected to the above pretreatment was subjected to steel plating and further solder plating under conditions E and F.

In this case as well, no peeling of the resist was observed in the cellophane tape peeling test.

Comparative Example 1 A laminate was prepared in the same manner as in Example 1 using a solution prepared with the following composition (photopolymerizable layer thickness: 40 μm).

B-14 (prepared in Reference Example 16) 200?
Trimethylolpropane triacrylate 220
tbe/siphenon 8t Michler's ketone 0.8t benzotriazole 0.8t p-methoxyphenol 0.13? diamond resin blue p
29 Ethyl acetate 50
0? Using the same method as in Example 2, a through-hole board was laminated and a tenting land test was performed, and the results were as follows: 8 7t-.

Tenting I 8 pieces Tenting 15 pieces La / Do I 40
Individual und l 52
Furthermore, a plating test similar to that in Example 18 was conducted, but the cured photosensitive layer on both sides of the image after plating was 0.1 to
Q: Peel off with a width of 5mm.

Example 19 Trimethylolpropane triacrylate 220? A laminate of 7 tons was obtained in the same manner as in Comparative Example 1, except that 140 tons of the sample was replaced with the same amount of C-1, and this is referred to as t-L-19.

Examples 20 to 35 Using the dry film resist laminates obtained in Examples 2 and 4 to 17 and 19, plating operations and resist plating resistance tests were conducted in the same manner as in Example 18. The results are shown in Table 4.

The results of the plating pretreatment, plating conditions, and tape peeling test in the table are listed in the annotations of Table 4 and are 9 and 10.

Table 4 A-C-E B-C-E A-D-E 20L-2aab 21L-4baa 22L-5aab 23L-6bbb 24L-7aaa 25L-+1aba 24L-9aaa 27L-10aab 28L-11aab 29 L-12b b b 50L-13a a H 31L-14a a b 32 L-15a b b 33 L-16b a 1) S4L-17aab 35L-18abb (Note) Plating pre-treatment conditions> Condition A: Manufactured by MacDamitsu [Lsnj 5G% aqueous solution [
After immersed in 40C for 3 minutes, immersed in 15% am/monicum persulfate aqueous solution for 1 minute, and further in 2% diluted sulfuric acid for 2 minutes Condition B: Diafloc company "Okite 90" in 5% aqueous solution at 50G for 2 minutes, 4A / dm After electrolytic degreasing at a current density of ', plating conditions were immersed in 15% ammonium persulfate aqueous solution for 1 minute and then 2 minutes in 20% diluted sulfuric acid VC> Condition C: Japan Metal Finishing Co., Ltd. "Copper sulfate conc" was immersed in 19% sulfuric acid. Plating is performed in a plating solution diluted 3.6 times at a current density of 2.57 L/dm' at room temperature for 30 minutes.

Condition D: 5 of “Pyrodonko/Ri” manufactured by Bursho Hampou Co., Ltd.
Plating is carried out at a current density of 2.5 A/d for 50 minutes at 55C in a 0% aqueous solution.

Condition E: Plating was carried out for 10 minutes at a current density of 2 A/d using a blind plating solution (tin/lead = 4/6) produced by Makdamatsu Co., Ltd.

(tape peel test evaluation) a; The resist does not peel off easily.

b: Parts with a width of 100μ or less and a length of 1m or less were peeled off here and there on both sides of the image.

Comparative Example 2 Using the laminate prepared in Comparative Example 1, a plating resistance test was conducted in the same manner as in Example 18. The plating conditions and tape peel test results are shown below.

Plating conditions Tape peel test results A-C-E
The resist peels off on both sides of the image line in a width of 100-200μ and a length of 3-5 iris.

B-C-E Both sides of the drawing line VCl50~2507! O
The resist peels off with a length of 4 to 10 cm.

A-D-E 3 with a width of 5G to 180μ on both sides of the drawing line
The resist peeled off at a length of ~5m+11.

Claims (1)

[Claims] A photopolymerizable laminate comprising a photopolymerizable layer and a support layer, and optionally a protective layer on the other surface of the photopolymerizable layer, wherein the photopolymerizable layer has (1 ) 5 to 95% by weight of a binder consisting of a vinyl polymer or vinyl copolymer (2) The value of molecular weight/number of double bonds contained, represented by the following general formula (A), (B), or (C), is 1000 or less A photopolymerizable compound characterized by containing 95 to 5% by weight of a photopolymerizable unsaturated compound whose main component is a photopolymerizable compound that is (3) 0.01 to 30% by weight of a photopolymerization initiator. laminate. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (C) [In the formula, n is an integer greater than or equal to 0, m is an integer from 3 to 10,
R_1 is hydrogen or a methyl group, X is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or ▲a mathematical formula, chemical formula, table, etc.
is an integer of 1 to 10, q and r are each an integer of 1 to 4), R_2 is an alkyl group having 1 to 6 carbon atoms or CH_2-O-R_4 (here, R_4 is a phenyl group,
aryl group or alkyl group having 1 to 6 carbon atoms),
Y is a divalent hydrocarbon group having 2 to 16 carbon atoms, Z is -(
CH_2)_t-O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (where t is an integer from 2 to 10, x is an integer from 1 to 30), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, Z_1 is -(CH_2)_t-O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas , there are tables, etc. ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼), W is ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, and W_1 is ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where W_2 is a trivalent hydrocarbon group having 3 to 10 carbon atoms, and s is an integer of 1 to 5). ]