JPS60140233A - Polymerizing composition - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymerizable composition containing a polymerizable material and a photopolymerization initiator for polymerizing the material, and particularly to a polymerizable composition used as a resist of a dry film. Regarding.

A family of dry or tack-free film resists is described, for example, in US Patent No. JF42. It is well known in the electronics technology as described in the specification No. 2.

Typically, such resists are formed from a solid photopolymerizable layer supported on a thin flexible polymeric support film and covered by a protective or cover film.

Recently so-called permanent or non-peelable dry film resist lines have been developed in which the cured photopolymerizable layer is exposed to the harsh atmospheres that the resist film is exposed to during the manufacture of printed circuit boards. can withstand. The use of a durable dry film resin (Mt) eliminates an additional step during the manufacture of printed circuit boards, ie, the removal of cured resin.

According to the present inventor's findings, it is possible to form a particularly durable resist film of a dry film by using a suitable photopolymerization initiator system and an ori-/'i- as a base. can be formed.

According to the invention, (a) at least one polymerizable olefinically unsaturated oligomer, which may be m-shaped or branched, wherein the oligomer has a repeating unit (Ar'-CHRl), where Ar'' is Each of the aromatic groups in the oligomer main chain may be the same or different, and each of the groups W in the oligomer main chain may be the same or different and contain hydrogen or a substituted crocodile conductor. hydrocarbyl group) and (1:) the acyl group contains a pendant and/or terminal acyloxymethyl group derived from an olefinically unsaturated carboxylic acid (hereinafter referred to as "aromatic/aldehyde" for convenience). Φ) a polymeric binder containing one or more polymeric binders; and (C) a photoinitiator system for initiating the polymerization of at least one aromatic/aldehyde oligomer. A polymerizable composition is provided.

Said aromatic group Ar'' may be monocyclic, e.g. phenylene, or fused polynomial, e.g. 7talene or anthracene, or preferably has the structure
It has Y1---. -φ-yl-φ-, where φ is a phenylene group ib, and y'' is a direct bond between λ phenylene groups or a divalent residue containing one or more molecular silver atoms; Each of the atoms can be carbon or a different atom and added to this can be 7' (7 or more atoms t+-, for example -〇+, -
S+.

or substituted derivatives of -CH,- or -CH,-, such as groups that activate the aromatic nucleus for electronic reactions, such as -〇- and -S-, "J)" is a group that activates the aromatic nucleus for electronic reactions. (for example, -SOr and -CO-).

Of all the substituents that may be present on aromatic groups! Lower alkyl groups having up to 1 carbon atoms, such as methyl and ethyl; lower alkoxy groups, such as methoxy, and halo groups, such as chloro.

Preferably, R1 in the repeating unit +Ar'-CHR1+ is hydrogen. However, this does not exclude the possibility that k can be an aryl group such as phenyl, an alkaryl group such as tolyl; an aralkyl group such as benzyl or an alkyl group having up to 6 carbon atoms.

The aromatic/aldehyde oligomers used in the present invention preferably have a functionality between 3 and 6, more preferably between 3 and 6. At functionality smaller than λ, curing of the polymerizable composition is too slow; at functionality greater than t, the cured product is often too brittle.

"Functionality" refers to the average number of pendant and terminal groups on each aromatic/aldehyde oligomer molecule.

In the aromatic/aldehyde oligomer used in the present invention, in which the aromatic group Ar'' has the following structural formula -1-ylφ-, the ratio of para-para bonds to ortho-para bonds is !:l and 2=7.

What is a "para-para bond"? The 10HR1- group is bonded to both phenylene groups in the residue -φ-Y1--- at the A12 position to the bonding part that is bonded to the Yl-residue and phenylene group. means a bond that exists.

"Orthodontic bond" means that the yl-residue is connected to the residue-1-
10HRI- group is bonded to the first phenylene group at the position ortho to the position bonded to the first phenylene group in Y1---, and -ys-at residue -φ-Yl −
10) means a bond in which an IRI- group is bonded to another phenylene group at the para position relative to the position in which it is bonded to another phenylene group in --.

The aromatic/aldehyde oligomers used in the present invention, when mixed with the polymeric binders defined below in the proportions described below, are non-tacky compositions that exhibit temperature fluctuations during their useful shelf life. Preferably, the viscosity is such that the composition results in a composition that does not flow when stored at a temperature.

The aromatic/aldehyde IJ fmer used in the present invention has a number average molecular weight (Mn) between OQ and 1io.
It is preferred to have a weight average molecular weight (Mw) between o and 2!00.

The aromatic/aldehyde oligomers used in the present invention are European Patent Application No. 13307/λ series filed by the applicant. issue(
(a description of which is incorporated herein by reference).

The polymeric binder used in this invention, when added to a solution of at least one aromatic/aldehyde oligomer in a suitable solvent, increases the overall viscosity of such solution and causes a solid layer to precipitate from the reservoir. is a thermoplastic resin that tends to reduce the tackiness of

The polymeric binder is io, ooo −/, ooo, o
The molecular basin of oo is preferably λo, ooo~100.00
It often has a molecular weight of 0.

The polymeric binder used in the present invention has a Tp (glass transition temperature) of 20° C. or higher, preferably! It will be appreciated that it has a TP of θ°C to /20°C, preferably about 20°C, and good thermal stability and should not unduly adversely affect the rate of polymerization of the polymerizable composition. .

Using a polymeric binder having a Tyt of about 0°C,
Preparation of three-layer structures such as those described below under conventional manufacturing conditions of temperatures of about 100 DEG C. and processing conditions often provides polymerizable compositions that flow to form VCC laminates.

Examples of suitable polymeric binders include polystyrene, polymethyl methacrylate, polyvinyl acetate, polyvinyl butyral, Halofle x, among others.
x) J, r allop V y (Al 1 oprene
) J and polyvinylpyrrolidone. Preferred polymeric binders include polymethyl methacrylate or preferably a combination of methyl methacrylate and lower alkyls having up to 6 carbon atoms, such as ethyl and butyl, methacrylate or preferably acrylate, for example in a molar ratio of about There are polymers.

The polymeric binder is, for example, 30 times the polymerizable composition! /weight factor, preferably Fii z ~ λQ weight/weight factor.

The amount of polymeric binder used in the polymerizable composition of the present invention and its Tff are selected in view of the conditions under which the three-layer structure is manufactured from the polymerizable composition as described below. The use of large amounts of polymeric binder in the overlay tends to create flaky layers of polymerizable composition in the three-layer structure.

The polymerizable composition of the present invention comprises one or more materials carrying one or more polymerizable olefinically unsaturated groups that are copolymerizable with at least one aromatic/aldehyde oligomer. can contain. Such substances will be referred to hereinafter as "comonomers" for convenience.

Examples of comonomers that can be present in the polymerizable compositions of the invention and that contain one polymerizable olefinically unsaturated group include:
Readily available monomers selected from among the hydrocarbon-containing types such as styrene, ethers such as ttd ethyl ether; esters such as vinyl acetate, methyl methacrylate, ethyl ester acrylate, butyl methacrylate and λ- Mention may be made of ethylhexyl methacrylate and amides such as 8-vinylpyrrolidone and N-alkylacrylamide P.

Examples of comonomers containing olefinically unsaturated groups in a plurality of polymerization ratios that can be present in the polymerizable composition of the present invention include polymerizable initial polymers. Examples of such prepolymers include vinyl urethanes, such as those described in British Patent No. 1. J
, td, OA No. 3, No. 1. ≠41027 and No. 1
, 445 Plr, $ 2 / and DE 2≠71117; and diols, especially the reaction products of bisphenols and glycidyl alkacrylates, such as U.S. Pat. No. 5 ottt.
Mention may be made of the reaction products described in No. i2 and No. 13/72. The descriptions in the above specification are hereby incorporated by reference.

However, when present in the polymerizable compositions of the present invention, the comonomer is preferably a low viscosity compound containing a large number of polymerizable olefinically unsaturated groups. Examples of such compounds include polyhydrocarbon compounds such as diethylene glycol, trimethylolpropane and pentaerythritol (burka)acrylic esters such as triethylene glycol dimethacrylate and trimethylolpropane trimethacrylate. .

The photoinitiator system used in the present invention can be any of the known photoinitiators used to initiate the polymerization of polymerizable olefinically unsaturated monomers. Examples include, inter alia (a) a mixture of Michler's ketone and benzyl or preferably benzophenone in a weight ratio of, for example, about 1:1% (
b) For example in a weight ratio of approximately l:l.
(C) Mixtures of amines and ketones as described in US Pat. coumarin-based photoinitiator system%id) combination of saarylbisimidazole and leuco dye, (e) U.S. Pat. cyclohemusadienone-leuco dye system as described in IAy specification or preferably if)
Mention may be made of initiator systems based on dimethoxyphenyl-acetophenone (hensyl dimethyl ketal) and/or jetoxyacetophenone.

Raw photopolymerization initiator system used in the polymerizable composition of the present invention
is, for example, less than or equal to about io weight/% by weight.

Although this does not exclude the possibility that the polymerizable compositions of the invention may contain peroxy polymerization initiators, this is not preferred.

When exposed to actinic radiation at a wavelength that is absorbed by the photoinitiator, the optically polymerizable compositions of the present invention exhibit a contrast between the silvery and unexposed areas of the composition. interacts with the photoinitiator system. For example, if the polymerizable composition is colorless, coloring occurs in the exposed areas of the composition, or preferably, if the polymerizable composition is colored, the coloring disappears in the exposed areas of the composition. or change color. To generate such a contrast, the monopolymerizable composition preferably contains a photosensitizer system that absorbs the actinic radiation described above. Examples of such photosensitizer systems include, among others, leuco dyes such as crystalline iolet; fluoranes and compounds which generate acidification on exposure to appropriate actinic radiation, such as Ph.
.

The polymerization ratio composition of the present invention may contain pigments such as phthalocyanino green.

The polymerizable composition of the present invention contains, for example, a processing aid. Examples of processing aids include agents that act as at least one of the following ingredients: surfactants, flow modifiers, or antiblocking agents, among others. Some suitable drugs are technically circumstantial, among them 01i', (oF2ot"2).

0H20H2000 (OH21, 60H, or preferably silicone acrylate or more preferably 1 is silicone diacrylate.

The polymerizable compositions of the invention may contain particulate fillers such as silica. It will be appreciated that the presence of particulate fillers does not unduly adversely affect the properties of the monopolymerizable composition. However, the presence of particulate fillers is preferred.
It's not something.

The polymerizable composition of the present invention contains, for example, a suitable thermal polymerization inhibitor. Examples of such inhibitors include p-methoxyphenol, high-P quinones, alkyl- and ester-substituted hydroquinones, and non- and t-butylcatechols, among others. Such inhibitors are used in amounts up to a few percent of the polymerizable composition.

In a preferred embodiment of the invention, the monopolymerization ratio composition is (a)
z, t-r, one or more aromatic/aldehyde oligomers and (b) one or more methacrylate homopolymers or copolymers from 10 to 30 mol/wt.%. a photopolymerization initiator system for initiating polymerization of the polymerizable composition (c1) and optionally (d) the various additives described above;
The combined weight % of b), (c) and +dl is the total to.

%.

The polymerizable composition of the present invention is preferably used in the form of a three-layer structure in which a solid or non-adhesive layer of the polymerizable composition is interposed between an upper support film and a cover film. It's convenient. however.

This does not exclude the possibility that the polymerizable composition could be applied directly to a suitable Go game as described below, for example by deposition from a suitable solvent.

Examples of suitable polymers which may constitute the support film used in the production of durable dry film resist membranes include polyamides, polyolefins, vinyl polymers, cellulose or preferably polyesters, and preferably polyethylene terephthalate, among others. can be mentioned. Preferably, the support film is transparent to actinic radiation at the wavelength to be used to cure the photopolymerizable composition. Preferably, the support film is substantially oxygen impermeable. The thickness of the support film is j
can be between 1 and 200μ, for example 10μ~
It is 0μ.

Cover used in the production of durable dry film resist membranes
The film may be formed from the polymers listed above as being suitable for making support films. Preferably the cut film is comprised of a polyolefin.

Preferably, it consists of I-lyeethylene. The thickness of the cover film can be between jμ and 200μ, for example ~! It is 0μ.

When using the polymerizable composition of the present invention in a three-layer structure,
The composition is in the form of a substantially dry, tack-free layer having a thickness of, for example, 10μ to iooμ.

The polymerizable composition is preferably applied to the support film as a solution in a suitable solvent and the solvent is evaporated leaving a substantially tack-free solid layer, but the composition is heated and softened. The 6vc film is laminated to the solid layer to obtain a three-layer structure '5, without excluding the possibility that it could be applied to the support film in the same state.

Examples of suitable solvents capable of forming tack-free solid layers include methyl ethyl ketone, methylene dichlorothane, among others, which tend to improve the clarification of the solid layer.

Moreover, a solution of the polymerizable composition dissolved in /, /, /-trichloroethane is more stable than a solution of the composition dissolved in methyl ethyl ketone.

In use, the cover film is removed from the 13-layer structure and placed on the exposed surface of the solid layer of polymerizable composition in contact with a suitable substrate and applied to the surface of the substrate, e.g. using a resilient heated pressure roll. Laminate.

To produce a resist image (image), preferably
imagewise irradiation of the polymerizable composition with actinic radiation having a wavelength in the range of 0 nanometers, preferably in the range of 320 to 100 nanometers; removing the support film, e.g. by peeling; suitable washing; The resist film is developed by washing away the light areas with a solvent, leaving the substrate carrying the resist image embossed on the surface. If the resist image is to be used in so-called additive processing, it may be heated to a temperature in the range of, for example, 10°C to -10°C using C#) or conventional UV (ultraviolet) curing equipment. - Post-cure by 7cUV curing (
post-#air).

Said suitable cleaning bath agent is conveniently t, t, t-') IJ dichlorothane. However, it is possible to select a cleaning solvent based on the type of polymeric binder.
It is not something to be excluded. for example.

If polyvinyl butyral is present, the cleaning solvent may be, for example, methyl ethyl ketone; if a methyl methacrylate homopolymer or copolymer is present, the cleaning solvent may be, for example, 7 m' t , t -trichloroethane. and if polyvinylpyrrolidone is present, the cleaning solvent is, for example, cyclohexanone.

When a resist film is to be formed on the copper-treated surface of the substrate, the unprotected copper is removed using the so-called 4F) (Substra -
It will be appreciated that it can be removed by active) treatment. However, it is preferable to use the resist film as a durable, i.e. non-patterned, resist film by so-called additional processing, in which metals such as copper (t%) may be applied by electroless plating, and in some cases by electrolytic plating. For the deposition process, the photoresist is deposited on the bare surface of a suitable substrate between the regions, e.g. a ceramic plate or a conventional substrate used for additive plating, e.g.
technology@00 - Deposit onto the bare surface of an epoxy glass composite such as that used in the day addition plating process.

Preferably, the polymerizable composition of the present invention does not contain sulfur or other polymerized metals that may have a tendency to adversely affect the temperature of the resist when resist films produced from the composition are used in additive processing. There are many.

Resist films prepared from the polymerization ratio compositions of the present invention can withstand (a) hydroxide solution for 20 hours at pH/co and lOe for % post-curing;
Withstands chromic acid for 1 month at yo℃ without distortion y2
% humidity and without blistering or loss of adhesion.
It is often able to withstand a solder float test for 30 seconds at 1°C (b) and resist attack by methylene chloride for 1 minute at room temperature with little or no change in surface hardness or appearance. It is.

According to another aspect of the invention, therefore, a method for producing a non-strippable pourable resist film on a surface.

The next step is (a) applying to said surface (a) at least one polymerizable olefinically unsaturated aromatic/aldehyde oligomer and (b) one or more polymeric binders. and (c) a photoinitiator thread that initiates polymerization of at least one polymerizable olefinically unsaturated aromatic/aldehyde oligomer. The other surface of the #1 solid layer shall be adhered to a thin flexible polymeric support film, and then the following steps (B) and (C) shall be performed in either order: ( b) Image-wise exposing the solid layer to actinic radiation to form a polymeric image in the layer.

(c) Peeling off the support film from the layer and then)
A resist image of the polymeric material (X) is completely formed by washing away the unlighted areas of the layer.

Kano 9 A method for producing a non-stripping resist film is provided, which is characterized by post-curing a resist image.

The invention is further illustrated by the following examples.

Example 1 This example describes the aromatic/aldehyde oligomers used in the present invention. Explain the production of mar.

sulfuric acid (specific gravity t) with stirring in an atmosphere of 1% oxygen in nitrogen at room temperature.
, zzo', ko3 point 2-), and the mixture was heated to 43°C.
Heat to. Methacrylic acid (io.

ppm of hy-r-quinone and /00 ppm of Topanol [stabilized with OJ 71C;
t i 7 Z ) f to the mixture followed by methacrylic acid (
Add a solution of L7t diphenyl ether (21#) to the solution over 30 minutes. Add the reaction mixture to
Stir for 3 h at 7°C and then leave for it min. Phase separation occurs, the upper organic layer is collected, sodium nitrite (t 00 ppm based on methacrylic acid) is added and t
Wash with water (i!Obx, 2) at o°C. When left to stand, it separated into a lower oligomer phase and an upper methacrylic acid phase.

The lower oligomeric phase was cooled to about 30 °C, washed with 0/% by volume aqueous methanol, and diluted with methylene chloride (rOz).
Dissolve in. The solution was analyzed for residual acid content and 7
Slowly add 0% excess of 10% 0% ammonia to the solution. An emulsion is formed and this is mixed with methanol (sob>
Addition of 100% to 100% and leave overnight to cause destruction.

The lower layer from the broken emulsion is passed through a small sieve column. Evaporation of methylene chloride leaves aromatic/Ryordehyde P oligomer (≠th> 1Mn=272:M
-=2/4A4A: Acid value/JqKOH/f; 'I7
(dliJ/'InyKOH/V; Hypoxyl number j/TagKOH/r; Functionality J, !7:
Ratio of parapara coupling to orthogonal coupling ≠, J:
/.

These examples illustrate the preparation of solid, tack-free adhesive layers of the polymerizable compositions of this invention.

A solution of an aromatic/hydrogen oligomer, a polymeric binder, a photoinitiator system and, if formulated, a comonomer, a dye, a pigment, a stabilizer, and an antiblocking agent in a suitable solvent. is applied onto a Melinex® polyester support film. In Examples λ-1, the support film has a thickness of 70μ, and in Examples 1-13, the support film has a thickness of 23μ. In Examples 2 to 2, a wet film coil wire application rod with a thickness of iooμ was used.
Example 10-V/! In this case, a wet film coil wire application rod with a thickness of 2 μm is used. The wet film is dried with a hot air blower and then left to stand for 2 hours at room temperature; a tack-free solid layer of polymerization ratio composition with a thickness of about 3 jμ supported on a polyester support film is obtained.

Composition of the non-adhesive solid layer (w/w %) and the solid layer 2
The deposition solvents are shown in Table 1 below. In addition to the weight% shown in Table 1, in the example, o,7M amount/weight% of Dopanol "O" (registered trademark) and 0,'/weight fik/weight ik%
of the silicone acrylate (Epecryl 3jO®); in Examples 1O to 13, 0.2% of the silicone acrylate and 701) l)m of the defoamer (Silcolapse 1130®) were present. In Examples 12 and 13, where TE/Oppm of benzoquinone was present, a polyethylene film was laminated to the bare surface of the tack-free solid layer using a hot roll laminator at 40°C. A three-layer structure is formed. Example? Now, polyethylene cuckoo film is laminated onto the bare surface of the tack-free solid layer using the nip rollers of a pilot coater at room temperature.

The cummer films in Examples 2-y are easily removed from the three-layer structure if necessary.

The solid layer with a tack-free ratio obtained in Example 10 was bright;
The solid layer in Example 11 was cloudy, and in Examples 12 and 13 the solid layer was almost bright.

Symbol A used in Table 7: Aromatic/aldehyde oligomer prepared as described in Example 70 of European Patent Application No. 133071λt.

B: Aromatic/aldehyde oligomer prepared as described in Example j≠ of European Patent Application No. 13307λr, z.

0: Aromatic/aldehyde oligomers with Mn=2-20 and functionality 3.2 as described in European Patent Application No. r33o7ico1.1.

D: M-1=Z00 and functionality 3.0, European Patent Application No. 1 JJO71 Co1. Aromatic/Ryordehyde P oligomers as described in Specification No.

E: Aromatic/aldehyde oligomer as prepared in Example 1.

F: Vinyl urethane prepared as described in European Patent Application No. t≠toyA except that methyl ethyl ketone was used as the reaction solvent.

I: Jetoxyacetophenone J: Ethyl Hiroshi-dimethylaminobenzoate (Quanta Chunia EPD®).

K': t-butylanthraquinone.

L: J,J-dimethoxy-λ-phenylcetophenone (Irgacure≦!/).

M: Michler Ketone.

N: Benzophenone.

0: N-N-dimethyl-λ-7minoethyl methacrylate.

P: Methyl ethyl ketone (4' of solution, w/w %).

Q: i,i,i-trichloroethane (Kenkuren®; %w/w of solution).

R: j I: ! : 44 / : Gunkrene (registration side 1/methylene chloride P mixture (3 g weight of solution/weight Y,) in a volume ratio of j.

W: Mn = J t, j 00 and Mw = 72
．． λ00 and methyl methacrylate polymer (Cryloid (registered trademark) B4'41').

X: Copolymer of methyl methacrylate and butyl acrylate in a weight ratio of T:l, Mn=lIJ200 and Mw=t j 000.

Y: Polymethyl methacrylate Mn=12000°z: Triethylene glycol dimethacrylate.

EXAMPLE 1 These examples illustrate the production of durable dry film resist films using the method of the present invention.

The exposed part of the non-adhesive layer produced in Examples λ-13 was subjected to initial storage for a period of time at room temperature.
A layer of Dynachem® Type 300WK@ Example 14 I-~λO using gold l
Laminated at lOj°C at a running speed of 7 ft; Example-
21 was laminated at a speed of i, s ft/min at ioz°C; Examples
℃ to form a complete laminate consisting of the plate, non-adhesive layer and support film.

This laminated body was left to cool for 30 minutes, and then melinex (
Stauffer (registered trademark) placed on the film
ultraviolet rays (Parker Grap) through one step (-2/-5tep) of the
hics'"Countess" exposure equipment has two MLUJs.
Equipped with a Philips Ultraviolet Lanzo of 00 Watts for a period of time.

After exposure, the resist film is stored for a period of time and then
(Registered Trademark) Period after removing the film and forming the non-adhesive layer/
, / , / -washed with trichloroethane; the wash-resistant cured resin was washed in the step wedge shape (5tep w) shown in the table.
It was obtained in the following stages including the stage shown in the edge number.

Table λ a: Not measured.

Examples 1 to 2Vf are repeated, but without the strafing step wedge, omitting the cleaning step after removal of the Melinex II film, and using a Philips HPR/JJW mercury discharge at a distance of %aO-. The electrocuring layer 7 is post-cured by exposing it to an electronic copying lamp for an hour (Example 1 to J/) or for an hour (Examples Coco to Cota).

The post-cured layer was unaffected by the presence of three drops of methylene chloride honey on its surface for three minutes.

The plate and post-cured layer are immersed in multi-core rosin foam flux Po, 24. After flux treatment,
The first part is 21j'Q with the resist surface facing downward.
No.2 O: μO placed on a tin-lead solder bath for 30 seconds;
The part was placed on the solder bath for 4 seconds with the resist surface facing downward.

j/second and contact for an additional 4 seconds. The first part and the λth part @t, i, l-)! After cleaning with J dichlorothane, it was found that the resist film had not lost its luster and had no blisters. A diagonal shading pattern with a width of -2IaI was created on both parts, and 7M's Scotch (registered trademark) was applied.
A piece of 4/0 Teizo is firmly pressed onto the surface of both resist films and removed by pulling quickly. Less than j% of the resist M was removed from the board.

Example 1≠~λ/i is repeated, except that a standard photoforming mold (photo-1ool) placed on Melinex® film and with a line-to-line spacing of 170μ is used.
) to make the laminate dark between sessions. 2 from the end of exposure
After 0 minutes, the Norinex® film was removed and the solid layer 't/, 1. Wash with /-trichloroethane for 1 minute: A resist pattern consisting of lines and spaces of approximately /70 μm is thereby formed.

Claims (1)

[Scope of Claims] /, (a) at least seven polymerizable olefinically unsaturated aromatic/aldehyde oligomers; (b) / or more polymeric binders; and (C) at least one polymeric binder; A photopolymerization initiator system for initiating polymerization of a polymerizable olefinic unsaturated oloaromatic/aldehyde oligomer. λ, at least 7 polymerizable olefinically unsaturated aromatics/
The aromatic group in the aldehyde oligomer has the following structural formula: %formula% ("where φ is a phenylene group and yl is a direct bond between λ phenylene groups or one or more molecular silver atoms. , each of which may be a carbon atom or a heteroatom and may have seven or more atoms appended thereto) The polymerizable composition according to claim 1. 3. The polymerizable composition according to claim 2, wherein Yl is oxygen. Hiroshi, at least one polymerizable ethylenically unsaturated aromatic/aldehyde oligomer is derived The polymerizable composition of claim 1, wherein the aldehyde is formaldehyde. !, the aromatic/aldehyde oligomer has functionality 1IIIi between λ and 6. Sexual composition. t, aromatic/aldehyde oligomer beams OO to 1ioo
Claim 7 has a number average molecular weight (Mn) of /700 to 2100 and a double tray average molecular weight (Mw) of '(i-
The polymerizable composition described in . 7. The polymerizable composition according to claim 7, wherein the polymeric binder is a homopolymer or copolymer of methyl methacrylate. 1. The polymerizable composition according to claim 1, wherein the photopolymerization initiator system is dimethoxyphenyl-acetophenone and/or jetoxy-acetophenone. ri, (a) j! -11 summer / weight of one or more aromatic aldehyde oligomers) lQ ~ 30
(c) a photoinitiator system and optionally (d) various additives;
The polymerizable composition according to claim 1, wherein the combined weight ratio of the components (a) to (d) is 100% in total. 10. (a) at least one polymerizable olefinically unsaturated aroma i (b) seven or more polymeric binders; and (C) at least one photoinitiator system for initiating polymerization of the polymerizable olefinically unsaturated aromatic/aldehyde oligomer. A three-layer structure comprising a polymerizable composition interposed between a support film and a cover film. //, (a) at least one polymerizable olefinically unsaturated aromatic/aldehyde oligomer; (b) one or more polymeric binders; and (C) a photoinitiator system that initiates the polymerization of at least one polymerizable olefinically unsaturated aromatic/aldehyde oligomer. a polymerizable composition of the invention is applied to a support film to form a substantially tack-free solid layer on one surface thereof, and a cover film is then laminated to the substantially tack-free solid layer. A method for manufacturing a three-layer structure, with lλ, 1 non-peelable dispersion on the surface). (b) one or more polymeric binders and (C) at least seven polymerizable olefinically unsaturated aromatic/aldehyde oligomers; 'fr: applied to a first surface of a solid layer of a polymerizable composition comprising a photoinitiator system to initiate the polymerization, and another surface of the solid layer is a thin flexible polymeric support film. and then the following steps (→ and (c) shall be carried out in any J [introduction, forming a polymeric image; (c) peeling the support film from said layer; and then) washing away unexposed areas of said layer to form a resist image of the polymeric material; and (c) forming a resist image of the polymeric material. A method for producing a non-peelable resist film, which comprises post-curing.