JPS6189846A - Novel photopolymerizable laminate - 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 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 create a printed circuit board using DFR, after removing the protective film, the copper-clad i
f (DFR is laminated on a permanent image forming substrate such as a laminate, exposed to light through a mask film, etc.).Next, the support film is peeled off as necessary, and the unexposed areas are photopolymerized with a developer. The resist composition is dissolved or dispersed and removed to form a hardened resist image on the substrate.Hereinafter, the process of forming a circuit can be roughly divided into two methods.The first method is to form a circuit that is not covered with hardened resist. After removing the copper peaks by etching, the resist is further removed.The second method is to perform a plating process such as )/da on the same copper surface, remove the resist, and then etch the copper peaks that appear. It is something.

In addition, in a printed circuit board produced using DFR, a conductive circuit forming material layer attached to the inner peripheral surface of the through hole,
For example, in most cases a thin steel film layer electrically connects one side of the permanent imaging substrate to the other. The manufacturing method for this type of printed circuit board is as follows:
The copper through-hole method and the solder through-hole method are common, and among the copper through-hole methods, the tenting method is becoming widely adopted. In this tenting method, both openings of the through-hole are completely closed with a photo-cured layer at the same time as the exposure-hardened arrangement image is formed, and when etching the steel thin film etc. to form wiring,
Since the photocuring 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 through hole.

The conductive circuit-forming material layer on the inner circumferential surface of the through-hole is limited in width 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 often supported by a band-shaped portion having a very narrow width. This tent-like supported photopolymerizable 1
Because each processing solution is showered during development and etching, there is often damage to the exposed photopolymerizable layer and damage to the permanent image forming substrate.
:? Therefore, the photopolymerizable layer of DFR used in the tenting method is required to have mechanical strength after exposure, adhesion to a permanent image forming substrate, chemical resistance, etc.

By the way, the photopolymerizable layer of DFH, which is currently widely used, contains an unsaturated compound (hereinafter referred to as a monomer) that has at least one ethylenic group and can form a polymer with a photopolymerization initiator (2). Consists of a thermoplastic organic polymer binder (hereinafter referred to as binder), +31 photopolymerization initiator, and (41) other additives (q! .

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, the binder should be selected from materials that are compatible with the binder, such as polymethyl methacrylate, methacrylic ester, acrylic ester, copolymers of acrylic acid, methacrylic acid, styrene, etc. is used.

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, but the monomers have a large influence on the composition, and the use of the monomers described above Mechanical strength, chemical resistance, and adhesion to the substrate after exposure of the photopolymerizable layer are not necessarily sufficient if the photopolymerizable layer is thin, and especially when used in the tenting method, the photopolymerizable layer is It needs to be thick.

On the other hand, there is an increasingly strong demand for electronic components and elements to be mounted in high density and to miniaturize the entire product. ing.

To form this high-density printed circuit, the DFH used must have high resolution, but the thicker the photopolymerizable layer, the lower the resolution. Therefore, when forming an image by using a DFR comprising a photopolymerizable layer as described above in a tenting method, 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 today to form printed circuits, uses an etching-resistant metal, such as solder, to protect the conductive circuit material layer, such as a copper 11AQ 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 substrate covered with the image-formed hardened resist layer is first subjected to pretreatment such as degreasing by alkaline cleaning, degreasing by surfactant aqueous solution cleaning, electroless copper plating, and further copper coating. Receives 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. In addition, the copper plating resistance, stain resistance, and pretreatment chemical resistance of the exposed photopolymerizable layer are also affected by the type of monomer and binder in the photopolymerizable layer, and in particular, the type and amount of monomer are controlled. influence. As a monomer, an acrylic ester or a methacrylic ester having only an ester bond or an ester bond and an ether bond, such as trimethicyl propane triacrylate as shown above or polyethylene glycol diacrylate, was used. The photopolymerizable layer has particularly good copper plating resistance,
Solder plating resistance and pretreatment chemical resistance are insufficient.Also, as an improved method for making printed circuit boards using DFR, films in which the support layer is dissolved or dispersed in the developer of the photopolymerizable layer are used. A method is known in which the support film is removed simultaneously during development processing without peeling off the support film after exposure using a DFR consisting of C%. This method has major advantages such as avoiding partial destruction of the image that can occur when mechanically peeling off the support film, shortening the process, and enabling continuous automatic processing. .

(Problems to be Solved by the Invention) As mentioned above, acrylic acid or methacrylic ester having only ester bonds or ester bonds and ether bonds, such as trimethylolpropane triacrylate and polyethylene glycol diacrylate, The photopolymerizable layer used has particularly poor copper plating resistance, solder plating resistance, and pretreatment chemical resistance. Also, in the improved tabulation method for printed circuit boards, the above-mentioned 7-mer is used as a monomer in the photopolymerizable layer,
If the DFR is laminated onto the substrate at an excessively high temperature and under a strong tension, fine cracks may occur in the laminated DFH support film, which is undesirable.

(Means for solving the problem) Considering the above background, copper through-hole method and solder through-hole method, both of which have good mechanical strength and excellent plating resistance after exposure, are extremely precise. As a result of our efforts to develop a photopolymerizable laminate that enables the production of explosive printed circuit boards, we have discovered the laminate of the present invention.

The present invention provides a photopolymerizable laminate comprising a photopolymerizable layer and a support layer, and optionally a retaining layer on the other surface of the photopolymerizable layer, in which the photopolymerizable layer is composed of II+vinyl Binder consisting of a polymer or vinyl copolymer 5 to 95 polymers (21) Photopolymerizable unsaturated compound containing a compound represented by the following general formula (4) 95 to 5 polymers (31 Photopolymerization initiator) This is a photopolymerizable laminate characterized by containing 0.01 to 30% by weight.

R,0 Y is -CM! -C)I, -C)ircH-CM, -CH
, -CHrCH, -, ■CH1-?・R4CH.

t -O-CHrCH, +0-C-CH! -CI! , -CH
,-CI(,-CH,÷,0R4 CB.

tCR3 R, CH, R.

n is an integer from 0 to 5, m is an integer from 1 to 10! number, t
is an integer from 1 to 20, p is a number from 1 to 5, R1*
R1 is hydrogen or a methyl group, R8 has a carbon number of 1 to 8
In the divalent aliphatic hydrocarbon group, R4 represents an allyl group or a phenyl group. ] Next, the laminate of the present invention will be explained in detail.

For Pine Dash, thermoplastic polymers consisting of polymers or copolymers of vinyl monomers are used, and among them, polymers of monomers represented by the following structural formula (B),
Or a copolymer consisting of them is preferred.

[In the formula, vl is hydrogen or methyl group, ■, is 7en20
〇 or an alkyl group having 1 to 10 carbon atoms, or a vinyl group). ] More preferably, polymers or copolymers of methyl methacrylate, methyl acrylate, butyl acrylate, styrene, butadiene, etc., which have good solubility in halogenated hydrocarbons, are preferred.

The molecular weight of the binder is 20.000 in weight average molecular weight.
or soo, oooO is preferable, and even s
o, o o o to 300,000 are preferred. If the molecular weight is too large, the development time becomes longer, which is not preferable. On the other hand, if the molecular weight is too small, the mechanical strength of the cured resist will decrease, which is not preferable.

Among the unsaturated compounds represented by the structural formula (A) [hereinafter referred to as monomer (2)], X is preferably a hydrocarbon group of -0-R, -12 or 4. In addition, it is preferable that the alcohol of the type X-OH becomes a secondary alcohol, for example, 10H as R1! -('H-CI(.

is particularly preferred. R is preferably hydrogen from the viewpoint of polymerizability. +CH for 2! -) 0- or ÷CM,
-CH-0÷ is preferable.

t Furthermore, the monomer (4) preferably has a ratio of molecular weight/number of double bonds contained of 1000 or less, and preferred values of m, t, p, etc. are determined by oneself.

Next, one example of the method for producing these seven snails will be briefly described.

Among the seven polymers represented by the structural formula (4), the figO one is a raw material shown by the structural formula (D) below, and X-01(CD+) 4-incyanatomethyl-1,8 - Reacting octamethylene diisocyanate (hereinafter referred to as TI)
More can be obtained.

Here, when a diol represented by the following structural formula (D,) is further coexisted, a 7mer represented by the structural formula (A) where n is 1 or more is produced, but at this time, a diol having nm Q is also produced at the same time. generate.

HO-Z -H(Dt) In this case, TI and diol (D,) are first reacted to form an incyanate oligomer, and then the diol (D,) is reacted with the inocyanate oligomer.
D,) is preferably added.

Here, as a preferable specific example of Nanatsuma (Dl),
2-hydroxyethyl acrylate, polyethylene glycol monoacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2
-Hydroxybutyl acrylate, 2-hydroxy-5
-Phenoxy acrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, acryloxyethyl-2-hydroxyglobyl-7-thaleate, methacryloxyethyl-2-hydroxyglobyl-7-thaleate, bis(hydroxyethyl)
Examples include phthalic acid monoacrylate, pentaerythritol triacrylate, tris(hydroxyethyl)incyanuric acid diacrylate, and the like.

TI, which is a triisocyanate, is disclosed in, for example, JP-A-56-
No. 127!541, it is obtained by reacting 1,8-diamino-4-aminomethyloctane or its bulk with phosgene.

Representative examples of diols (D,) include ethylene glycol, propylene glycol, butanediol, hexanediol, and diols represented by the structural formula (D,).

OR, OR.

In the formula, % R1 is hydrogen or methyl; 2. As, 1,000C
H! −)0−1÷CH, −CH−0+ is preferable.

m + t (where m and t are integers from 1 to 10) The reaction is preferably carried out in a solvent, and aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl propionate, a7tone Ketones such as , methyl ethyl ketone, and methyl isobutyl ketone are preferred. Although the reaction can be carried out either in the absence of a catalyst or in the presence of a catalyst, it is desirable to use a catalyst in order to carry out the reaction quickly. As this catalyst, for example, tertiary amines such as triethylamine and triethylene diamine, and tin compounds such as stannath octoate and dibutyltin dilaurate are used.

In addition, the reaction operation is carried out in the carbon-
It is desirable to carry out under conditions where carbon double bonds do not polymerize.
For this purpose, the reaction temperature is 80C or less, preferably 50C.
It is as follows. Further, it is desirable to conduct the reaction while blocking active light.

Furthermore, 1 active hydrogen group per 1 incyanato group itK
It is preferable to carry out the reaction at a temperature higher than this time to eliminate free isocyanate groups.

The following 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 (D,) or DI
4).

In the formula, 2. is hydrogen, methyl or halogen, Z.

is 7enyl, vinylphenyl, cyano, halogen, pyridyl, imidazolyl or -''-0-24 (Za 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, a dialkylaminoalkyl group having 5 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a tetrahydrofurfuryl group, a halophenyl group, a carpitol group or hydrogen), such as styrene. ,
Divinylbenzene, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and ethyl acrylate, isopropyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, carpitol acrylate, acrylic acid Acrylic acid esters such as methoxyethylene glycol, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acrylic tetrahydrofurfuryl, 2-chloroethyl acrylate, acrylic rn2゜3-dibromopropyl, tribromophenyl acrylate, acrylic allyl, etc. or corresponding methacrylic esters, vinylpyridine, vinylimidazole, etc.

RI OOR+ In the formula, ZS is a divalent alkyl RIR having 2 to 10 carbon atoms.
.

is an integer from 1 to 20, R1 is hydrogen or methyl), Examples of the monomer (Ds) are bentanediol, hexanediol, ethylene glycol, tetraethylene glycol, nonaethylene glycol, polyethylene glycol, neobentanediol and diacrylates and dimethacrylates of diols such as polygummy pyrene glycol.
trivalent alkyl group, trivalent alkoxy having 6 to 14 carbon atoms Examples of monomers (DI) which are already defined include trimethylolpropane triacrylate, tri(acryloxypropoxy)
hexane, tri(acryloxypropoxy)propane,
tri(hydroxyethyl)triazine acrylate and the corresponding methacrylic acid ester.

In the ceremony, 21 to z1! At least 3 of them are hydroxyl groups, and 1 is 0 or 1.

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

R, -CmCH,R, -010M.

In the formula, z13 is divalent alkyl having 1 to 8 carbon atoms,
j is an integer from 2 to 6, and an example of the monomer (D) is "Aronix" manufactured by Toagosei Chemical Industry Co., Ltd.
can be mentioned.

In the formula, z14 is an alkyl group of -L10 having 1 carbon number, hydroxyalkyl it having 1 to 6 carbon atoms, or -C)I,
-N! 'I-C-C (j), where R1 is hydrogen or methyl.

Examples of monomers (D,) include acrylamide, methylenebisacrylamide, N-1-butylacrylamide, N-1-octylacrylamide, N-methycoolacrylamide, N-butoxymethylacrylamide,
and the corresponding methacrylamide.

OR.

In the formula, %R is hydrogen or methyl.

In the formula, z+s is hydrogen or an alkyl group having 1 to 10 carbon atoms, and examples of -(DIS) include cinnamate acid, ethyl cinnamate, propyl cinnamate, etc. 1: In the formula, zllll Examples of hydrogen, phenyl or -(n,t) include maleimide, phenylmaleimide, diphenylmethane bismaleimide and the like.

In the formula, % RleZl has already been defined.

R1 is hydrogen or methyl, and n is an integer of 1 to 4.

Furthermore, it is particularly preferable to coexist a monomer represented by the following structural formula (Book 9) or (G), and this urethane-based monomer may become a product of the unsaturated compound component.

(XO-C-NH-)W (2)+1' [In the formula, %X-2 is already defined, qF'io or more is a number of 10, r is an integer between 5 and h and 10, Y is carbon Number 2
represents a divalent hydrocarbon group A having 1 to 16 carbon atoms (bird represents a trivalent hydrocarbon group having 3 to 10 carbon atoms). ] mo/-r-(E) to (G) are h-(, X is preferably X such that X-OH is a secondary alcohol.

Examples of the photopolymerization initiator or photosensitizer 1 that can be used in the present invention include benzoin, benzoin alkyl ether, polynuclear quinones such as anthraquinone, benzophenone, chlorobenzophenone, Michler's ketone, fleonone, thioxanthone, dialkylthioxanthone, and halogenated thioxanthone. , dimethylamine inamyl benzoate, ethyl dimethylbenzoate, naphthalenesulfonyl chloride, azobisisobutyronitrile, 1-azobis-
1-Cyclohexanecarbonitrile, 2,4-dichlorobenzoyl peroxide, diphenyl disulfide, dibenzothiazole, 1-(4-isopropylphenyl)
-2-hydroxy-2-methylpropan-1-one, 2
-human oxygen 2-methyl-1-phenyl 1o pan-
1-one; dyes and adult donor substances such as erythrin, triethylamine, p-butanebenzoic acid esters, triphenylphosphine, 2-2-dimethoxy-2-phenylacetophenone, and the like. These photoinitiators or photosensitizers may be used alone, or
Two or more types may be used in combination.

The weight fraction of these essential components relative to the total photopolymerizable layer is:
The binder is 5 to 95%, preferably 20 to 80%, more preferably 30 to 70%. The total monomer amount is between 95% and 5%, preferably 8%.
It is 0 to 20%, more preferably 70 to 30%. The content of photopolymerization initiator is 0.01 to 50%, preferably 0.1 to 15%, and further KtFf″1
or 1 to 10%.

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

Although the thickness of the photopolymerizable layer varies depending on the application, it is 5 to 150 μm, preferably 5 to 70 μm for producing printed circuit boards, and the thinner the layer, the better the resolution.

The support layer used in the photopolymerizable laminate of the present invention may be transparent or opaque to actinic light, but consideration should be given to the labor of the image forming process and prevention of dust adhesion during exposure. A transparent material that transmits active light is desirable.

The support layer that transmits active light includes polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl copolymer film,
Polyvinylidene chloride film, vinylisochloride/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 both the support layer and the unexposed areas of the photopolymerizable layer without peeling the support layer from the photopolymerizable layer is as follows: It has advantages such as process simplification and image stability, but if the photopolymerizable layer of the present invention is applied, it can be used even under severe lamination conditions without causing cracks in the support film. . In this case, the support needs to be a material that can be dissolved or dispersed in a solvent that can dissolve or disperse the photopolymerizable layer. When the developing liquid is an organic solvent, polymethacrylic methyl film, methyl methacrylate copolymer film,
Particularly preferred are polystyrene films, styrene copolymer films, etc. When the developing liquid is aqueous, polymer films containing amino groups, ammonium groups, hydroxyl groups, carboxyl groups, and these groups, such as polyvinyl alcohol films, cellulose derivatives, etc. is preferred.

Although the protective layer is not an essential constituent, it must be easy to peel off from the photopolymerizable layer, and therefore it is preferably a polystyrene film, a polypyrene film, secophane, polyethylene terephthalate treated with a release agent, release paper, etc. .

The photopolymerizable layer of the present invention is cured by exposure to actinic rays, and here, active rays refer to visible light, ultraviolet θ, and electron beams, and light sources include the sun, arc lamps, mercury lamps, and high-pressure mercury lamps. , ultra-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, and is suitable for both the steel through-hole method using the tenting method and the solder through-hole method using plating, as described above. A printed wiring board can be produced with extremely good results by a conventionally known method using photopolymerization ff/1.

In the tenting method, high mechanical strength of the cured film,
It was found that damage to the through-hole closing film during development or etching was significantly less, reflecting the adhesiveness with the substrate. As an unsaturated compound of the photopolymerized laminate, structural formula (
Compared to the case of using monomers shown in C to C),
When the monomer represented by structural formula (4) was added or replaced, a photocured film having even greater tenting strength could be obtained. In the solder through-hole method, the plating solution did not penetrate into the interface between the resist and the substrate during plating, demonstrating good plating resistance. Further, since the uncured photopolymerizable layer can be completely removed by development, etching and plating can be performed extremely uniformly. Furthermore, this photopolymerizable 1-
has high photosensitivity and also shortens the exposure time 4t61.

The photopolymerizable composition of the present invention also has better solubility in halogenated hydrocarbons such as 1,1.1 + )lychloroethane, which are commonly used for DFR development, than those containing general urethane acrylates.

That is, by using the integrated photopolymerizable layer of the present invention, it is easy to produce a printed circuit board with high density variation and high elliptical density.
Furthermore, there is an advantage that the printed circuit board manufacturing process can be simplified. Further, 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 1 168 4-(isocyanatomethyl)-1,8-octamethylene diisocyanate (hereinafter abbreviated as TI) was added as inocyanate to a 2-volume four-volume flask equipped with a dropping funnel, a thermometer, and a stirrer. ? Then, a mixture of 780% dry methyl ethyl ketone as solvent 1, 2862 2-hydroxypropyl acrylate as dibutyltin dilaurate as solvent and 65f methyl ethyl ketone as solvent 2 was added dropwise so as not to exceed the internal temperature of 35 Ct. After dropping, stirring was continued for 30 hours at 40C, and in the infrared absorption spectrum, the characteristic absorption of the incyanate group near 2270α''1 almost disappeared, making sure to confirm the following points. Next, add 50 tons of methyl ethyl ketone as solvent 3. This reaction product is designated as C-1.

Reference Example 2 Add 'l'11002 to the Yotsuro flask used in Reference Example 1.
and dibutyltin dilaurate 0.35 as catalyst
? Then, 70 ft of ethyl acetate was added as solvent 1, and 200 t of borietele/glycol (average molecular weight 200) as compound (D) was added dropwise over 2 hours while stirring. During this time, adjust the temperature and speed of the water bath to ensure that the internal temperature does not exceed 40C. Furthermore, 40
After stirring for 1 hour at
I dripped 0Ci super big brother. After that, 48 at 40C
After stirring for 9 hours, 1002 ml of ethyl acetate was added as solvent 2 to form a homogeneous solution. This will cost ¥1-C-2.

Reference Examples S to 5 TI and the following polyhydric hydroxy compound were reacted under the reaction conditions shown in Table 1 to obtain a TI prepolymer.

・Polycarbonate; molecular weight t250. OH value 90 (
(hereinafter abbreviated as PCL) ・Polyglobylene glycol; molecule 5k1000, OH
Value: 110 (hereinafter abbreviated as PPG)/1,3-butanediol (hereinafter abbreviated as 1,5-BG) The obtained prepolymers are respectively referred to as C-3 to C-5, and the physical properties are also Table IK is also listed below.

Table 1 1) Dibutyltin dilaurate 2) Measuring gutter viscosity Nimira rotational viscometer 5) Measuring method NCO content: Measured according to JIS K-1556.

8 Example 6 2-hydroxyethyl acrylate (2-HEA) 166 Ll as the monomer (DI) and T·1100 f (NC010H equivalent ratio 1.
2) and dibutyltin dilaurate (DBTDL)0
, 1t as a catalyst at 50G for 2 hours.9. At this time, 0.02 ff of hydroquinone monomethyl ether (Q) was added as a thermal polymerization inhibitor.

The obtained urethane acrylate was a highly fluid transparent liquid with a viscosity of 700 cps at 25C. This is called C-6.

Reference Examples 7 to 12 Urethane acrylates were synthesized according to the method of Reference 1+116. Table 2 shows the formulation, reaction conditions, and physical properties of the obtained urethane acrylate.

These 1 (referred to as -7 to C-12).

In addition, the abbreviations in Table 2 indicate the following.

2-HEA: 2-hydroxyethyl acrylate 2-H
PA: 2-hydroxypropyl acrylate 2-H
EMA: 2-hydroxyethyl methacrylate FA
-1: e-caprolactam 1 adduct of 2-hydroxyethyl acrylate [Daicel Chemical Industries, Ltd.] PETA
: Bentaerythritol triacrylate MEK : Methyl ethyl ketone Reference Example 13 A urethane acrylate solution was prepared in exactly the same manner as in Reference Example 1 except that hexamethyl diisocyanate was used as the inocyanate. This is called C-13.

Reference example 14.

In the same flask as in Reference Example 1, add 35% 2.4-) lylene diisocyanate and 77 tons 80? Add 0.64 ffil of dibutyltin dilaurate and 2-hydroxypropyl acrylate 5561 and 215 and stir.
77 tons of gold mixed solution of f was added dropwise, and stirring was continued for 25 hours. During this time, the internal temperature was adjusted so as not to 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 nine samples were analyzed by gel permeation chromatography, and no adduct of tolylene diinocyanate and ethanol was observed. It was confirmed that the tolylene diinocyanate was consumed in the reaction and the reaction mixture was designated as C-14.

Reference Example 15 1 was placed in a three-volume Mitsuro flask, propylene glycol diglycidyl ether diacrylate (Denacol acrylate manufactured by Nagase Sangyo Co., Ltd.) DA-911: hydroxyl equivalent: 22
2) Add 97.71 and the above (-14280t1 diptyltin dilaurate o, sy, a7ton 7Sf,
The reaction was continued for 4 hours at 50C under magnetic stirring, and then for 12 hours at 45G, and the completion of the reaction was confirmed by infrared absorption spectrum. This product is designated as iC-15.

Reference Example 16 Stirring: Test, put the fA flow condenser FT 95 into a separable flask with ion water exchange at 2000 rt,
Methylcellulose (yi Etsu Chemical Metrose 5R-10
0) 10 t of sodium chloride was added as a solution layer, and while stirring at 75C, methyl methacrylate was added as a 7-mer.
80f and butyl acrylate 20? , azobisinobutyronitrile2. Next, 1 t of Sf and dodecyl mercaptan (D homogeneous mixture) was added. After about 1 hour, the internal temperature began to rise and reached ?OC.

After lowering the internal temperature to 80C, take a water bath for 2 hours and stir at 90C for 1 hour, then pour the contents into a 300 mesh gold pluie and wash with a sufficient amount of water.As a result, A bead-shaped polymer with a particle size of 100 to 400 microns was obtained and dried, and designated as polymer iB-16. Analysis of this B-16t-gel permeation chromatography revealed that the weight average The molecular weight is 176,000.

Example 1 B-16-1 (49f, mo/-r) was added as a binder to a 7 tsaa-capacity separable flask.
- as C-14Of and C-1313? .

Benzophenone 2T and Michler's Gato 7G as initiators
, 2f, Dai 7 Resin Blue P (Mitsubishi Chemical Corporation M) as a dye, and benztriazole 0.0 as an additive.
2F, 30 da of p-methoxyphenol, and 4 ff of ethyl acetate as a solvent were added and stirred for 15 hours to obtain a coating solution. Next, the above coating solution was completely coated on a 20 μm polyethylene terephthalate film as a support layer using a blade coater, and air-dried for 50 minutes.
dried in the oven. The thickness of the resulting photopolymerizable layer is 4
0μ and nine. Next, this photosensitive layer is coated with 25% as a protective layer.
μ polyethylene film was laminated with a pressure roll (
Then, while peeling off the polyethylene film, apply 80C to the silk-covered glass epoxy laminate.
pressurization. Next, pass the negative mask film all the way through this laminate using an ultra-pressure mercury lamp (Oak Seisakusho Fenikx 50 GO type) K! J1cid 9100m
Next, perform exposure with JO dose. Next, peel off the polyethylene terephthalate film and use a spray nozzle to
1,1,1-) When dichloroethane was sprayed for 100 seconds to dissolve and remove the unexposed areas, a good image 11 was obtained.
! (This is called a resist image) 1- Obtained.

It was confirmed that the resolution was 40μ. Next ・50Co
Ferric chloride solution was sprayed for 2 minutes to fx latch the exposed copper surface, but no image flow was observed.

Example 2 A 10-ton separable flask with a leaking stirrer and reflux condenser was charged with methacrylic resin (Delpetsu 70H, manufactured by Asahi Kasei Corporation) 1940? as a binder. , put in 3000 t1 of methyl ethyl ketone as a solvent, stir at 70C to dissolve, and then dissolve as C-12212
f% Benzophenone 80f5 as initiator Michler's Ketone Bf, Diaresin Blue P2G as dye
? , benzotriazole 8? , 1.3 f of P-methoxyphenol was added, and after stirring for 6 hours, this solution was coated on a 20 μm polyethylene film as a protective layer using a coating machine, and the solvent was dried.
After forming a photosensitive layer with a thickness of 5μ, 1
The laminate was wound into a roll while being covered with a 5μ stretched polystyrene film.

This laminate is called L-2. Next, using two of these roll-shaped laminates and a printed circuit board laminator, a through-hole board (a copper-clad glass epoxy board with 1064 holes of 4.0m diameter perforated at 4.011 intervals) was fabricated with through-holes. A laminate substrate was obtained by adhering and laminating nine photosensitive layers supported by polystyrene while keeping a polyethylene film T41 on both sides of the substrate (all parts of which were also copper plated).

At this time, the heating roll of the laminator was set at 80CKθ.

Using this laminate board JLC ultra-high pressure mercury lamp, 10
After 9 days of 0 mJ/cdi irradiation, ' * 1 *
1-) IJ dichlorothane was sprayed for 120 seconds, a developing operation was performed, and the number of breaks in the cured film on the through holes was counted, but no breaks were observed (this test was called Tenting-I).
).

Next, after development, the substrate was etched for 2 minutes by spraying a 50C ferric chloride solution, but no tearing was observed (this test is referred to as tenting-■). Next, using another laminate substrate, it was exposed to light from both sides through a land mask under the above conditions to form a cured film with a diameter of 4.6n on both sides of each through hole.
A test similar to I. Land each exam ■,
Land ■ was used, but no holes were observed in either case.

Comparative Example 1 A laminate was obtained in the same manner as in Example 2 using a solution prepared with the following composition (photopolymerizable layer thickness: 40 μm).

B-14 (prepared in Reference Example 16) 200?
Trimethylolpropane triacrylate 220
t Benzopheno 7 8 t Michler's Ketone 0.8? Benzotriazole 0.8tp-methoxyphenol 013f Dia Resin Blue p
2f ethyl acetate
5002 In the same manner as in Example 2, it was laminated onto a through-hole board, tenting and land tests were performed, and the results were as shown in Table 3.

Table 3 Test Tenting number of tear holes! 8 pieces tenting■ 1S piece land 1 40
Example 3 The coating solution prepared in Example 2 was applied to the treated side of a silicone-treated polyethylene terephthalate release film using a blade coater tube, dried, and photopolymerized to a thickness of 44 to 45 μm. After forming the adhesive layer, cover with the same release film. This film is S Om / m x 5 m /
? After cutting into film and exposing it to x light at a predetermined exposure dose, the two release films were peeled off, and the maximum stress and elongation at break were measured using a tensile tester. The tensile speed was Filogi/min. The results are shown in Table 4.

Table 4 Comparative Example 2 The same operations and tests as in Example S were performed using the coating solution prepared in Comparative Example 1. The thickness of the photopolymerizable layer was 44 to 4.
It was 6μ. The results are shown in Table 5.

Table 5 60 2So 62 1on 255 90 Examples 4 to 11 Using the same apparatus as in Example 2, a dry film resist laminate was formed in the same manner. Table 6 summarizes the names and amounts of the raw materials used, the thickness of the resist layer, the protective layer, and the support.

For each example, 7 t g of monomer and binder combined
Add 0.2 parts of benzotriazole and 0.05 parts of p-methoxyphenol to convert the resist solution to A.
I arranged it. The obtained laminates are respectively designated as L-4 to L-11.

In addition, in the implementation LyTI5.8+', unlike Example 2, a photosensitive layer was formed on the support layer, and after 7'2:
The M film was laminated with gold to form a rolled laminate. In these cases, as in Example 10, the support film was peeled off by hand before development. Table 7 also shows the results of the tenting and ground tests.

(Monomer) M-1; Toagosei Higaku Kogyo Co., Ltd. N “Aernics M-305J (Main component: Bentaerythritol)
Retrieved from
) M-2; 1'-D-3S OJ manufactured by Nippon Kayaku Co., Ltd.
(Main ingredient: Dipentaerythritol triacrylate -
) M-5; Kyoeisha Yushi Kagaku Kogyo Co., Ltd., "Epoxy Ester 70PAJ (Main component: Pufpyrene glycol diglycidyl ether/acrylic acid adduct) M-4; Osaka Organic Chemical Industry Co., Ltd., "Visco-) 57
00J (Main component, bis(1,5-bentanediol) phthalic anhydride-acrylic ester) (Binder) g-1 Asahi Kasei Corporation Delvera) 15ONB
-2 Delpet CR-IB-5 manufactured by the same company
Made by the same company Delvet 70HB-,,a
Asaflex AF made by the same company
X-810 (initiator) i-12,4-diisopropylthioxanthone 1-24
-(dimethylamino)isopropylbenzoate 1-5
Benzophenone 1-4 4.4'-(dimethylamino)benzophenone 1-5 Fluolein I-6 dimethylbenzyl ketal (dye) D-1 Mitsubishi Chemical Corporation! JJ @Blue-P
'″D-2 Company 'tJ
”Green-C”D-s same company”
:J”Blue-K”D
-4 Company 'El'
BJu6-Q'' (Hokyu 1 layer) P Oriented polypropylene (20μ) E Polyethylene (38μ) (Support) S Oriented polystyrene (15μ) T Polyethylene terephthalate (20μ) Table 7 Example 12 A tear in Example 1 The obtained material L-1 was pressed onto a copper-clad glass laminate using an 80C pressure roll while peeling off the polyethylene film, and this laminate was exposed to light using a 17-step step tablet as a mask, followed by polyethylene terephthalate. Peel off and use a spray nozzle to apply 1,1
．． 1-) Develop by spraying dichloroethane for 100 seconds, and then create a number of tablet stages in which photopolymerization remains completely. Hereinafter, this number of stages is defined as "1 sensitivity".Table 8
shows the exposure amount and sensitivity.

Comparative Example 3 Using the coating solution prepared in Comparative Example 1, all operations were carried out in exactly the same manner as in Example 12. The results are shown in Table 8.

Examples 13 to 20 Examples 4 to 11 - Represented by nine fRJ integral L-4 to L-11
Perform the same operation as in Example 12 using .

In addition, in the case of L-4, L-6, L-7, L-10, and L-11, the protective layer is peeled off while the laminate is coated with a laminate. eL, developed for 115 seconds without peeling off the support. The results are shown in Table 8.

Example 21.22 Laminated bodies L-1 and L-2 obtained in Examples 1 and 2) L7t! The stretched Jn body was exposed to light at a dose of 80 mJ/d through a positive mask film. Then, it was developed with '+'*'-) dichloroethane, and then it was immersed in an aqueous solution of VC from Macdamid Corporation for 5 minutes, washed with water, and treated with an aqueous ammonium persulfate solution and dilute sulfuric acid.
2 at 20C. ! +A/d go current vi Takumi for 30 minutes 1■,
Sulfuric acid steel plating was performed. Missing number, 2A/dr! Solder plating was carried out for 10 minutes at 7°C.As a result, the flow of thin wires was barely visible, and sellotape was applied on the tij image, and after three sufficient layers, the pre-plate was peeled off. However, no peeling of the resist was observed at all.

Comparative example 4

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 made of a vinyl polymer or vinyl copolymer (2) 95 to 5% by weight of a photopolymerizable unsaturated compound containing a compound represented by the following general formula (A) (3) Photopolymerization A photopolymerizable laminate comprising 0.01 to 30% by weight of an initiator. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (A) [In the formula, ▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Z is -(CH_2)-_mO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, There are chemical formulas, tables, etc. ▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Z_1 is -(CH_2) -_mO-, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ n is an integer of 0 to 5, m is an integer of 1 to 10, l is an integer of 1 to 20, p is 1 to 5 integer, R_1,
R_2 represents hydrogen or a methyl group, R_3 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R_4 represents an allyl group or a phenyl group. ]