JPS6385538A - Photosettable laminated body and picture image forming method using thereof - Google Patents

Abstract

PURPOSE:To improve the alkali resistance of a dry film type photoresist by using a compd. contg. a specified recurrent structural unit as an essential component for a photosettable layer. CONSTITUTION:A photosettable layer contg. a copolymer comprising the recurrent structural units expressed by the formulas I and II as essential components is formed on a substrate (e.g., polyester film). In the formulas, R0 is vinyl, epoxy, or episulfide; R1 is H, 1-6C alkyl, halogen; W, X, Y, Z are H, halogen, cyano, 1-6C alkyl, 1-6C haloalkyl, etc. In addn. to the above described copolymer, a thermoplastic resin, photosettable compd., and photosensitizing agent, etc., may be added to the photosettable layer. By this constitution, a resist material having high alkali resistance is obtd., which is effectively useful for the formation of a circuit basing on a semiadditive process.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel photocurable laminate and an image forming method using the same, and more specifically, to the production of printed circuit boards and printing original plates. and a photocurable laminate useful for forming a protective film, etc., which has particularly excellent acid resistance and alkali resistance, and a resist image formed on the surface of a substrate for permanent image formation using the photocurable laminate. The present invention relates to a novel method for forming .

The permanent image forming substrate as used in the present invention refers to one in which a resist image formed on the surface of the substrate is used as a protective film and an image is formed on the substrate itself by etching or plating, or one in which the resist image itself is formed on the substrate. The examples are copper-clad laminates, metal plates, glass films, etc. Furthermore, a resist image is an image formed on a substrate surface by photopolymerization of a photopolymerizable compound.

[Conventional technology]

Currently, printed circuit board manufacturing methods can be roughly divided into the following three methods. The subtractive method uses a resist image formed on a copper-clad laminate as a protective film to create a predetermined circuit by etching, etc., and the subtractive method involves forming a predetermined resist image on an insulating plate and chemical Examples include the full additive method, in which a circuit is formed by plating copper, and the semi-additive method, which is an intermediate method between the two. Among these methods, the subtractive method is currently the mainstream, but with the technological trend of increasing demands for higher density and higher reliability of substrates, it is becoming more and more popular to use high aspect ratio holes, small diameter holes, etc. Semi-additive and full-additive methods are rapidly attracting attention because they have the disadvantage that through-hole plating is undesirable, and one manufacturing process is long and complicated. On the other hand, a wide variety of photocurable resist materials have been developed according to each method, and various properties are required for use in printed circuit board manufacturing. These properties include not only lithography properties such as sensitivity and resolution, but also properties such as heat resistance, mechanical strength, aging resistance, and alkali resistance. Among these, electroless plating bath resistance, especially high alkali resistance, is important.

Conventionally, photocurable resists that can be used in additive process processes, especially dry film photoresists for semi-additive process processes, have not had sufficient performance, resulting in problems such as displacement of the resist image from the substrate during plating, peeling, etc. Also as a developer.

/, / -) Lichloroethane cannot be used,
It has problems such as low resolution and is not suitable for use.

[Problem that the invention seeks to solve]

In light of these technological trends, the present inventors have conducted intensive studies and found that electroless copper has excellent acid resistance, alkali resistance, heat resistance, and mechanical strength, and is peelable, especially since it has high alkali resistance. We have discovered a photocurable laminate that is effective in the process of forming circuits by plating and a method for forming a resist image on a permanent image forming substrate using the photocurable laminate, and have achieved the present invention. I arrived at the eggplant.

[Means for solving problems]

The present invention consists of a photocurable layer and a support, and the photocurable layer comprises a compound containing repeating structural units represented by the following structural formulas [A] and [B] [hereinafter referred to as compound (a)]. ]
The present invention relates to a photocurable laminate characterized in that it contains as an essential component.

Yo-〇(A) (B) [However, [In the formula A1, Ro represents a vinyl group, an epoxy group, or an episulfide group, and R1 is hydrogen or carbon! ll
Represents an alkyl group of numbers 7 to 2 or a halogen. Furthermore, R8 and Ro are substituted at the ortho, meta, or para position relative to the carbon atom of the main chain.

CB) In the formula, w, x, y and 2 are each hydrogen, halogen, cyan group, alkyl group having 1 to 2 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, and alkyl group having 1 to 3 carbon atoms. or an aryl group having 2 to 30 carbon atoms substituted with a halogenated alkyl group, an aryl group having 3 to 30 carbon atoms substituted by U containing a silicon atom, a aryl group having 1 carbon, 4 to 17) 7 carbon atoms,
-COOR2, -COR2, -〇-COR, (Rz is carbon!!'I&/&Ishi/co alkyl group or halogenated alkyl group, carbon v!, / or O's alkyl group or halogenated alkyl group An aryl group having from 2 to 30 carbon atoms substituted with l?? by a group containing a silicon atom.
a substituted aryl group having from 1 to 30 carbon atoms, or an aryl group having from t to 30 carbon atoms), a nitro group, a group containing a silicon atom, or R3 (Rs hydrogen, hydroxyl group, carboxyl group, halogen, Nitro group, amino group, cyano group,
Represents a substituent containing a hetero group substituted with a carbon alkyl group or a halogenated alkyl group, or an aryl group having 6 to 30 carbon atoms, or a group containing a silicon atom] Photocurable laminate of the present invention The photoborizing property j in the formula contains the compound (a) as an essential component, and generally contains 1 to 99% by weight, but it has seven components in terms of adhesion to the support and stability. Ishiqrijufchi is preferable, and more preferably! to 90% by weight, adhesion to the substrate,
Considering various physical properties such as chemical resistance,
% is a particularly preferred range.

The number average molecular weight of compound (a) is from roo to /,000
．． 000 is common, and 3.000 in terms of sensitivity and resolution.
to 5oaooo is preferred.

In formula (A) of compound (a), R1 may be hydrogen, an alkyl group having 1 to 2 carbon atoms, or a halogen, but hydrogen is preferable.

In formula (A), RO may be a vinyl group, an epoxy group or a thiiranyl group. In selecting these, the reactivity of each functional group and the physical properties of the resist image as a protective film after curing should be considered. For example, when adhesion to a permanent image forming substrate is required, epoxy or thiiranyl groups are common, and high sensitivity and mechanical strength are required! In this case, vinyl groups are common.

In formula [A), Ro is ortho to the carbon atom in the main chain,
It can be in either the meta or para position, but from the viewpoint of sensitivity, the meta or para positions are preferable.

It is not necessary to use only one type of repeating structural unit represented by the structural formula [A], but by using two or more types in an appropriate ratio, a resist with higher overall performance can be obtained that combines the characteristics of each type. You can make materials.

w, x, y and 2 in the repeating structural unit represented by structural formula (B) of compound (a) are each hydrogen, halogen, cyano group, alkyl group with carbon number / to t, or halogen with carbon number / to an alkyl group having 7 to 3 carbon atoms, an alkyl group having 7 to 3 carbon atoms or an aryl group having 3 to 3 carbon atoms substituted by a halogenated alkyl group, and an aryl group having 3 to 30 carbon atoms substituted by a group containing a silicon atom. group, aryl group having 2 to 30 carbon atoms, -COOR
,, -COR2, -OC0Rz (an alkyl group or halogenated alkyl group with Rz = carbon number / to /-, carbon number 6 to 30 substituted with an alkyl group or halogenated alkyl group) an aryl group, an aryl group having 6 to 30 carbon atoms substituted by a group containing a silicotactic atom, an aryl group having 6 to 3 degrees of carbon atoms), a nitro group, a group containing a silicon atom, or R
3 (R3 is hydrogen, hydroxyl group, carboxyl group, halogen,
Betero ring substituted with a nitro group, an amine group, a cyano group, an alkyl group or a halogenated alkyl group, or an aryol group having 6 to 3 carbon atoms, a group containing a silicon atom) Substituents containing may be used. less than,
Although these general examples are shown below, the present invention is not limited to #JJ.

Common examples of halogens include fluorine, chlorine, bromine, and iodine, and examples of alkyl groups having 1 to 2 carbon atoms include methyl, ethyl, butyl, hexyl, isopropyl, tere-butyl, and cyclohexyl groups. and
As a halogenated alkyl group with carbon number/to
Examples of allyl groups having carbon number ≦h and 30 include substituted phenyl group, f1-substituted indenyl group, substituted naphthyl group, substituted azulenyl group, and substituted azulenyl group. butarenyl group, substituted biphenylenyl group, substituted aS-indacenyl group, substituted 6-indacenyl group, substituted acenaphthynyl group, substituted fluorenyl u,
amm phenolyl group, substituted anthryl group, substituted fluoroanthryl group, substituted aceantrylenyl u'E'
1 m) Liphenylenyl group, substituted pyrenyl group, substituted chrysenyl group, substituted natsutacenyl group, substituted vicenyl group, q
t-substituted perylenyl group, substituted pentaphenyl group, substituted pentacenyl group, substituted tetraphenylenyl group, fdtx hexaphenyl group, r! monosubstituted rubicenyl group, substituted coronel group,
Examples of the silicon atom-containing group include (1) to (38) below, such as a ro-substituted trinaphthylenyl group, a substituted he/taphenyl group, a substituted hebutacenyl group, and a tQ-substituted pyranthrenyl group.

-8l (-CH* ・CaHs)s
Sl + C6Hs)3αd+
01) (b) (b)
(!To my sister)
06) αノ(ro))
(2))
(21) @ (c) (b) ni)ni)
(b) (b)
(b) Ko (52) (5th floor (9)
Iri (ro)
(@Furthermore, general examples of substituents containing a heterocycle substituted with R1 include (1) to 31) of the following structural formula group.

(4) (5) (a)I3 (b)) 0xun
(b) (+6) (17)
(Foundation) Martyr C: I! J) (B)
(b) Horse (suru) (ni) (b) (
(to) (→ (6)(
B) (G) (G) [
However, in each structural formula, n represents ViO or /, and R
sFi hydrogen, hydroxyl group, carboxyl group,...rogen, nitro group, amine group, cyano group, alkyl group with 1 to 2 carbon atoms, halogenated alkyl group, carbon-A number 2 to 30
The specific preferred combinations of w, )c, y and 2 (WIXIY, z) are shown in the form (H, H, H,
H), (H, H, H, C6Hs), (H+ H(H+
C6114-C2H5), (H,H,H.

Cl0H7), (H, H, H, Cl4H9), (H, I
I, CH3, C5Hs), (H.

CH3+ Hr CJ(4-5t(CH3)3), (
H1HLC6H5IC6H5)-(C6H5IIITH
, CaB6 ), (C8T(5,H,H,Cl0H
7)-(C6H%+HtHI Cl4H9'))(Cl
0H7+ H+ Hr C1o1b ), (H, H, H
, C00CHa'), (H,H,H.

coo CFs ), (H, TOCH3, C00CH3)
, (H,HlCI, C0CHs), (T(,H,H,
CN), (T(,H,H,C00C6H5),H,St
(CT(,)i), (H+H,H,5i(CsHs
)3) etc., and (H.

I(,H,)(),(HI Hl)(l C6H5)
, (Hr H+ H+ C6)I4- CzHs),
()I, H 1 + Cl0I(7), (H+ I
(*H+ CbHg), (H, T(, CI(3,
Cs Hs ), (II+ CH3+ H+ C6H4
-Si(CH3)3), (H,H,C5Hs,C
5Hs), (Cabs, H, H, CaHs), (
C6bs, )I, H, Cl0H7), (C8H
5+) (Not IHLed.

In addition, the repeating unit represented by the structural formula CB) does not have to be of one type, but two or more types can be used in an appropriate ratio. The overall performance as a curable layer can be improved.

The molar fraction of the repeating structural unit represented by the structural formula (A) of compound (a) is generally 99% to 99%, and preferably 91% to 99% from the viewpoint of resolution and sensitivity.

Next, a method for producing compound (2L) will be explained.

When Ro in structural formula (A) is a vinyl group, JP-A-56-
7 Otsu! No. 09, in the case of epoxy group, JP-A-Sho/;/-
223uO, and in the case of an episulfide group, it can be produced by the method described in JP-A-A/-3/μ09.

In order to make the present invention more effective, a thermoplastic W resin [hereinafter referred to as (b)] and a photocurable compound [hereinafter referred to as (.)] are added to the photocurable layer containing compound (a). It is preferable to contain.

At 9j:! to r:qs, preferably 10:30 to 3o, more preferably 70:30 to 3r
It is within the range of its.

Moreover, the total content ratio of components (b) and (c) in the photocurable layer is determined by the following formula.

WVc=100-Wa W.

W b/' c s Wa % WO ke total of each component (b) and (c), compound (-) and other containing layer'! Represents 1chi.

As the thermoplastic resin of component (b), (a) and (e
) components are preferably compatible with the photopolymerizable compound, such as vinyl polymers such as polymethyl methacrylate, methyl methacrylate copolymer, polystyrene, styrene copolymer, polyvinyl chloride, and vinyl chloride copolymer. Union,
Examples include polyvinyl acetate/vinyl acetate copolymer, polyvinyl alcohol, and cellulose derivatives. Among these thermoplastic resins, when halogenated hydrocarbons are used as the developing liquid, polymethacrylic methyl or methyl methacrylate copolymers or mixtures thereof,
Particular preference is given to polystyrene or styrene copolymers or mixtures thereof.

Component (c) of the photocurable compound includes (a) and (
Those that are compatible with b) are desirable, and examples of functional groups include acryloyl group, methacryloyl group, vinylphenyl group, allyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, maleimide group,
Those having a double bond such as a phenylmaleimide group, a vinylfuryl group, a vinylpyridyl group, a vinylimidazolyl group, an epoxy group such as a glycidyl group, etc. are desirable. These include cinnamate esters, maleimides, phenylmaleimides, bismaleimides, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, Acrylic acid esters such as dipentaerythritol tetraacrylate, dipentaerythritol triacrylate, acrylates of dicarbonate and diol or triol esters, tris(hydroxyethyl)triazine acrylate, or corresponding methacrylic esters, acrylamide, methylol acrylamide, N
-t-butylacrylamide, N-t-octylacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, diacetone acrylamide, 2-methyl-
Acrylamides such as 3-sulfoprobyl acrylamide and triacrylamide formal, but still corresponding methacrylamide, styrene, cyhinylbenzene, acrylonitrile, methacryloyl group, ethyl acrylate, inglovir acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate , -monoethylhexyl acrylate, lauryl acrylate, carpitol acrylate, ethoxynoacrylate, methoxypolyethylene glycol acrylate, λ-hydroquine ethyl acrylate, -monohydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, l1μm butylene glycol Monoacrylates such as monoacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, tetrahydrofurfuryl acrylate, 2-chloroethyl acrylate, 2,3-dibromopropyl acrylate, tribromphenyl acrylate, allyl acrylate, oleyl acrylate, and also bentanediol , acrylic or methacrylic esters of diols such as hexanediol, ethylene glycol, tetraethylene glycol, nonaethylene glycol, polyethylene glycol, neobentanediol, polypropylene glycol, neobentanediol ester of adipic acid, with the following structural formula ( I)(-(J(2
+n (representing an integer of nhl-r)], a diacrylate having the following structural formula (II) 0+C■■2-
Acrylate, acrylonitrile, α-chloroacrylonitrile which is an acrylic adduct of diacrylate 1 epoxy resin represented by Y, -〇-)-C-CH=CH2...(n) is an integer from / to , vinyl r: IJ resin vinyl imidazole, etc., but are not particularly limited to these. For example, monomers such as glycidyl methacrylate and styrene, polyfunctional heptamers having a styrene skeleton, or monomers having reactive functional groups such as epoxy resin can be used as components of the photocurable layer of the present invention. Moreover, these may be either liquid or solid at room temperature.

In the present invention, it is preferable to add a photopolymerization initiator and a photosensitizer for the purpose of shortening reaction time and curing time. The amount of addition of the photopolymerization initiator is less than the amount of JOIL in the photocurable layer, preferably 0.0 to 20% by weight.

Examples of the photopolymerization initiator or photosensitizer that can be used in the present invention include benzoin, benzoin alkyl ether,
Anthraquinone tri(r)poly-n quinones, pentuphenone, chlorbenzophenone, Michler's ketone, fleonone, thioxanthone, dialkylthioxanthone, halogenated thioxanthone, naphthalenesulfonyl chloride, azobisisobutyronitrile, l-azobis-7-
Cyclohexane carbonitrile 1.2. q-Dichlorobenzoyl peroxide, diphenyl disulfide, dibenzothiazole, /-(μm isopropylphenyl)-
2-Hydroxy-2-methylpropan-/-one, 2-
Hydroxocomethyl-/-phenylpropane-7-
On; erythrocinnato dye, π-donating substance, triethylamine, p-7 minobenfoate esters, triphenylphosphine 1. ! Examples include -j-dimethoxy λ-phenylacetophenone, and photoionic polymerization initiators are also effective. The photoionic polymerization initiator referred to herein is a compound that generates a Lewis acid or Brønsted acid using a photometric window. These photopolymerization initiators or photosensitizers may be used alone or in combination of one or more types. Additives such as dyes, stabilizers, and plasticizers may also be added.

The thickness of the photopolymerizable layer varies depending on the application, but for making printed circuit boards! -200μ, preferably j to 120μ; the thinner the thickness, the better the resolution.

The support used in the photopolymerizable laminate of the present invention may be transparent or semitransparent to high-energy radiation.

Supports that transmit high-energy rays include: polyethylene terephthalate, polyvinyl alcohol, polyvinyl chloride, vinyl chloride copolymer, polyvinylidene chloride, vinylidene chloride copolymer, polymethyl methacrylate, methyl methacrylate copolymer, polystyrene , polyacrylonitrile, styrene copolymers, polyamides, cellulose derivatives, etc., and plate-shaped ones.

As an opaque support, gold (aluminum, copper, lead, etc.) lul
i. Materials listed in the examples of supports that transmit high-energy rays may be treated to make them opaque.

The high-energy rays referred to here refer to ultraviolet light, deep ultraviolet light, laser light, etc. that can efficiently cure the photocurable M, and soft X-rays, electron beams, etc. can also be used to cure the photocurable layer of the present invention. The kC of curing is effective.

Next, an image forming method using a single photocurable layer will be described. That is, the following structural formulas [A] and [B]
A photocurable laminate consisting of a photocurable layer containing a compound containing a repeating structural unit shown as an essential component, a support, and optionally a protective layer is used as an image-forming material, and image-forming exposure is performed using high-energy radiation. The unexposed portions of the photocurable layer are then dissolved or dispersed in a developing liquid to form an image on the support. , (A) in the formula OR6, Rt and CB) in the formula w
1x, y, and z are the same as above] Examples of the developing liquid that can be used when dissolving or dispersing and removing the unexposed portion of the photocurable layer include acetone, ketones such as methyl ethyl ketone and methyl ibutyl ketone, and methyl formate. , esters such as ethyl acetate, butyl acetate, and amyl acetate, chlorinated hydrocarbons such as methylene chloride, chloroform, trichloroethylene, and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, and fraudulent ethylene. Examples include ether esters such as glycol monoethyl ether, 3-methoxybutyl acetate, and diethylene glycol monoethyl acetate, ethers such as diethyl ether, dioxane-tetrahydrofuran, and mixtures thereof. moreover,
Alcohols such as methanol, ethanol, isopropyl alcohol, and ethylene glycol monomethyl ether, hydrocarbons such as hexane and octane, and a poor solvent for the photocurable layer such as water can be mixed with the developing liquid.

〔Effect of the invention〕

The photocurable laminate of the present invention has high resolution due to good developability, and the cured film after exposure has mechanical strength, adhesive strength with a permanent image forming substrate, chemical resistance, and plating resistance. It is used as a photoresist material with particularly excellent alkali resistance, and has excellent performance in both the copper through-hole method and the solder through-hole method. It is easy and elegant, and has the advantage of simplifying the printed circuit board manufacturing process.

It is particularly effective in the process of forming a circuit by electroless copper plating, and a preferred embodiment of forming a circuit using the photocurable laminate of the present invention is to deposit the photocurable laminate on a substrate. After exposing and developing a desired pattern with high-energy rays, copper plating is performed using an electroless steel plating solution.Then, the resist image formed on the substrate is peeled off and a desired pattern is formed. An example is creating a circuit.

〔Example〕

Specific embodiments will be shown below with reference to Examples, but the present invention is not limited thereto.

The following synthesis examples and examples; The analytical apparatus and method used in Sanjisho are as follows.

GPC (gel permeation chromatography):
4 AN' ml per day = wyvssρT
'Ei' +41-・mu-103, A-10μ series,
Measurement of number average molecular weight using two standard polystyrene detection lines.

NMR (Nuclear Magnetic Resonance Spectrum): JEOL%
JMR-axuoo type ET-NMR (4!00 MH
z).

Synthesis Example 1 Synthesis of Govinylstyrene Oxide Into a /l reactor equipped with a stirrer and a thermometer, p-divinylbenzene (cojg), sodium hydrogen carbonate (daOg), and toluene (Hirooomt>) were added, and the internal temperature was was maintained at 5°C, and a toluene solution (too
After dropping 9.μ0 weight ichi), stirring was continued for 10 hours while maintaining the internal temperature at 5°C. After the reaction was completed, the reaction solution was washed with an aqueous sodium carbonate solution and dried over anhydrous magnesium sulfate. After removing the desiccant, toluene was distilled off under reduced pressure, and then purified by distillation to obtain gouvinyl styrene oxide (/Torrs 7 u'c). Collection QFitj
It was 9.

Synthesis Example 2 Synthesis of g-vinylstyrene episulfide Add 1 methanol (700 mA) to a /73 flask equipped with a stirrer and a thermometer, add 100 g of divinyl styrene oxide (100 g), and bring the internal temperature to joC. No 1-
While maintaining the temperature at 10°C, thiourea (3rg) was gradually added and stirred for 72 hours. After the completion of the reaction, methanol was removed by condensation distillation, and the residue was washed with water to obtain ψ-vinylstyrene episulfide (ta9) tr:IFJfc.

From the proton nuclear magnetic resonance spectrum of the product, the δ value is
7-~7. Yo, otsu, otsu j, j, 7 otsu, r, 20.3.9
! ~ζ/! , ko, 4Z at t~3.0, respectively, /, /,
, /S2 protons were observed.

Synthesis Example 3 l-methyl-7, cordiphenylstyrene (α-methyl-β-phenylstyrene) α-methylstyrene (10 m
mO1), palladium acetate CPd(OAc)2) (/
mmol) triethylamide 7 (/□mmol),
Add nitrile (soml) and phenyl iodide (9j mmol), add 3j at /OO'C
The reaction solution was heated and stirred for 70 hours, and then cooled.
After pouring into a heavy hydrochloric acid aqueous solution, removing insoluble matter and removing the solvent, it was purified using an alumina column. In the NMR spectrum of the obtained product, a δ value of 7.0 was observed.

Synthesis Example V To a /l separable flask equipped with a stirrer, a thermometer, and a reflux condenser, % purified toluene (uoorrd'J) was added, and the epoxy compound obtained in Synthesis Example 1
> and styrene (Hiroori) were added under stirring to form α, α′-
Azobisisobutyronitrile (0,00 g) was added, and stirring was continued under a nitrogen stream for an hour while maintaining the internal temperature at 77'. After the reaction was complete, the reaction mixture was poured into a large amount of methanol and overnight. The white precipitate was separated, washed with methanol, and then dried under reduced pressure at room temperature to obtain a copolymer.The yield was determined by R2. From GPC, the number average molecular weight was +7 t,000. Met.

Furthermore, it was found from the proton nuclear magnetic resonance spectrum of the 1-coelectrolyte that it contained 56 moles of epoxy compound.

Synthesis Examples J to 7 In Synthesis Example 3, copolymerization was performed using the monomers shown in Table/D in place of styrene to obtain copolymers shown in Table/D.

Synthesis example! A small flask equipped with a stirrer, a dropping funnel, and a thermometer was filled with 9 ml of dry tetrahydrofuran (SOO).
mt) and diisopropylamine (200 l), and
Cooled at 1 °C. Next, a solution of n-butyllithium in hexane was added dropwise with stirring.

1-2-vinylnaphthalene (3
s9), and a solution of p-divinylbenzene (/, S) in tetrahydrofuran (200Hd) was added to 30ml 17n
The addition was continued at a rate of r 2 and stirring continued under a stream of air for an additional 9 g hours. After adding methanol (3 ornl), the reaction mixture was slowly added into a large mouth of methanol, resulting in a white precipitate. This was taken from house to house, washed with water, and dried to obtain a white solid (7r). This white solid consists of acetone, acetic acid, toluene, and chloroform.
ic A +3 There was. The number average molecule determined by QpC was 31,000 Te:b. N MR spectrum has a peak around δ value O0l~3.0 Fukuhiro D
1 collection! ? , 0~j, 3 and j, r-J'J K slightly sharp absorption, O, θ~7. Otsu KS≦, 6 and 7.7
Broad absorptions with respective peaks were observed.

From the above relative intensity of absorption, it was found that 10 mol% of divinylbenzene was contained. Next, the compound obtained above (
To the mixture were added methylene chloride (30 ml), carboxylic acid (3.3 g), and the mixture was cooled. Metachloroperbenzoic acid <tg> was mixed with methylene chloride (o-
) was added dropwise with stirring, and then the reaction solution was diluted with
The mixture was kept at ℃ and stirred for 2 hours.

After confirming with iodized starch paper that the metachloroperbenzoic acid in the reaction solution had disappeared, the reaction solution was washed three times with a saturated aqueous sodium bicarbonate solution and dried over anhydrous magnesium sulfate. After discharging the drying agent, white powder (s, u9) was obtained by distilling off methylene chloride under reduced pressure. This was easily soluble in oral solvents such as toluene, methyl ethyl ketone, ethyl acetate, and chloroform. It was determined by GPC that fr, yM, average molecule Q1-ta, zoooo. The NMR spectrum has a δ value of O0t ~ around 3.0 K/
Broad absorption with peak at J, r, r, J,/, 3
．． r, ,t,,z and! , 7 slightly wide absorption, 6. o~7.7 to 4. A broad absorption with a peak of ≦ and 7.7 was measured.

Synthesis Example 9 A small flask equipped with a stirrer, a dropping funnel, and a thermometer was purged with nitrogen, and dried tetrahydrofuran (soom
t> and diisopropylamine (3009) and cooled to O″C. Next, a hexane solution of /!% n-butyllithium (/911 mA) was added dropwise with stirring.

9-vinylanthracene (uO) was processed while maintaining the temperature at 0 @CK, and a solution of p-divinylbenzene (≦O) in tetrahydrofuran (2oomt) was heated to 3 o mt.
The mixture was added continuously at a rate of Kr/hr, and stirring was continued under a nitrogen stream for an additional Kr hour. After adding methanol (3 ml), the reaction mixture was gradually added to Daikane's methanol, and a white precipitate was obtained. I got it. This white solid was easily soluble in acetone, ethyl acetate, toluene, chloroform, and the like. The number average molecular weight determined by GPCK was 0OO.

The NMR spectrum has a δ value of o, r ~ J, near O'/Cy
, broad absorption with a peak at r,! r, 0− j, J and j,! ~ Slightly sharp absorption in r, 1.0-7.6
Broad absorption with peaks at ≦, t and 7.7, respectively, was observed.

From the above relative intensity of absorption, it was found that ro mol% of divinylbenzene was contained.

Synthesis Example 10%l/, 12 A copolymer was obtained by carrying out the reaction in exactly the same manner as in Synthesis Example 9, except that the monomers shown in Table 1 were used instead of 9-vinylanthracene.

Synthesis Example 13 After washing with methanol, add Ey (20/r OV/V) to a /l flask equipped with a stirrer and a thermometer, and dissolve the copolymer (100 liters) obtained in Synthesis Example q. death,
Internal temperature! Thiourea (6
(original liquid) was gradually added, and stirring was continued for 72 hours. After the reaction is complete, the insoluble matter is removed from each house, and the same wave is then poured into a large amount of methanol.
4g) was obtained. The number average molecular weight determined from GPCK is y
From the O nuclear magnetic resonance spectrum of r, ooo, the epoxy group and episulfide group were each 2.33 mol% of lA.
It was found that it contained

Synthesis Example 7 μ Purified toluene (4!oOttrl) was added to a /l separable flask equipped with a stirrer, thermometer, and reflux condenser, and the episulfide compound (ψ09) obtained in Synthesis Example λ and styrene ( to'; l) under stirring,
α, α′-Azobisisobutyronitrile (/9) was added, and stirring was continued for 7 hours under a nitrogen stream while maintaining the internal temperature at 70″C. After the reaction was completed, the reaction mixture was poured into a large amount of Poured into methanol and allowed to evaporate overnight.

The white precipitate was separated, washed with methanol, and dried under reduced pressure at room temperature to obtain a copolymer. The yield was ≦r, and the number average molecular weight was -J,Q00 according to GPC.

Also, from the proton nuclear magnetic resonance spectrum of the copolymer,
It was found that 31 mol of episulfide compound was contained.

Synthesis Example 1, lt A polymer was obtained by carrying out the Kff reaction and post-treatment in the same manner as in Synthesis Example/II, except that the monomers shown in Table 1 were used instead of styrene.

Synthesis Example 17 A copolymer (yr9) was obtained by carrying out the reaction and post-treatment in exactly the same manner as in Synthesis Example Hiroshi, except that 3-vinylstyrene oxide (30%) and styrene (70%) were used as the epoxy compounds. From GPC, its number average molecular weight is 3
．． ooo, and from the proton nuclear magnetic resonance spectrum,
It was found that 25 mol% of epoxy groups were contained.

Synthesis Example it In Synthesis Example 9, p-divinylbenzene was replaced with commercially available divinylbenzene (i amount % in 1, m unit/p
Integral ratio 73;/2! ;) was used, the reaction and post-treatment and purification were carried out in exactly the same manner to obtain a copolymer. As determined by GPC, its number average molecular weight was 3/,000.

Example/-/≦ In a 11 separable 7 Lanuko equipped with a stirrer, component (a) which is an essential component, component (b) as a thermoplastic resin,
Component (c) as a photocurable compound, an initiator, a solvent, and, if necessary, a dye were added in the proportions shown in Table 2, and stirred for 75 hours to prepare each mixture.

Next, the mixture was applied onto a polyethylene terephthalate film having a thickness of 3 rμ as a support using a blade coater, and then dried in a hot air oven at 10° C. for 75 minutes. The thicknesses of the obtained photocurable layers are as shown in Table λ.

Furthermore, the photocurable laminate obtained above was pressed onto a steel-clad glass epoxy laminate using an lrO''C pressure roll.A negative mask film was passed through this laminate using an ultra-high pressure mercury lamp (Oak Seisakusho, Exposure was carried out using a Phoenix 3ooo type) with the irradiation shown in Table 3.
Table 3 Haha/-)lichloroethane using a spray nozzle
When spraying was performed for the time indicated in , the unexposed portions were dissolved and removed, and good images were obtained in each case.

Next, the image (100 100 μm square patterns × lOO
The pattern survival rate after immersing the substrate on which the pattern was formed was immersed in a sodium hydroxide aqueous solution VCLIO at pH/s and humidity 10''C was used as an alkali resistance test.The results are also shown in Table 3.

Ratio example/2 Using a mixture prepared with the following composition, image formation and alkali resistance tests were conducted in the same manner as in the examples.

The results are shown in Table 3.

Comparative Example/Composition of Delpet 70H,! 009 Trimethylol triacrylate, 2
20g benzophenone rg michler's ketone o, 1g dial cashier/blue
P λri M E K
Composition of 3009 Comparative Example 2 GP≦r3ro O (1 trimethylolpropane triacrylate) 1rOQ benzophenone? Kumihiraz Ketone
o, rri M E K
3009 (blank below) Note: (b) Component b-/ Asahi Kasei Corporation Styron GP≦
Ifeb-1 Asaflex AF manufactured by the same company
X-to.

b-J Mitsubishi Rayon Co., Ltd. Acrybet (
c) Component c-/ Manufactured by Toagosei Chemical Co., Ltd. (hereinafter abbreviated as Toagosei) [Aronix M-3osj (main component: pentaerythritol triacrylate) C-1 rD-330J (main component) manufactured by Nippon Kayaku Co., Ltd. ; dipentaerythritol triacrylate) c-3
"Epoxy ester 70PAJ (main component: propylene glycol diglycidyl ether acrylic acid adduct)" manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd. (hereinafter abbreviated as Kyoeisha Yushi) C-≠ Osaka Organic Chemical Industry Co., Ltd. (hereinafter abbreviated as Osaka Organic Kagaku) Jr Viscoat 370 (7) (Main component: Bis(/, J-bentanediol) phthalic anhydride-acrylic ester) c-! Kyoeisha Yushii "Epoxy ester BP-<c
PAJc-6 Toagosei Club “Aronix rloooJ
(Polyfunctional acrylic acid ester) Initiator 1-/-Lμm diisopropylthioxanthone 1
-2 ψ-(dimethylamino> rest number m isopropyl 1-J benzophenone ■-up, u'-(dimethylamino)benzophenone!
-4 Fluorine I -t Dimethylbenzyl ketal -7 Triphenylphosphine r -r tA-Chlorthioxanthone 1-q
Ethyl tl-(dimethylamino)benαzoate 1-10
'l-Chlorbenzophenone dye

Claims (2)

[Claims] (1) It consists of a photocurable layer and a support, and the photocurable layer contains as an essential component a compound containing a repeating structural unit represented by the following structural formulas [A] and [B]. Photocurable laminate. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [B] [However, in [A] formula, R_0 represents a vinyl group, epoxy group, or episulfide group, R_1 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen. Further, R_1 and R_0 are substituted at the ortho, meta, or para position relative to the carbon atom of the main chain. [B] In the formula, W, X, Y and Z are each hydrogen, halogen, cyano group, alkyl group having 1 to 6 carbon atoms, and 1 carbon number.
a halogenated alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms substituted by an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 30 carbon atoms substituted by a group containing a silicon atom; group, aryl group having 6 to 30 carbon atoms, -COOR_
2, -COR_2, -O-COR_2 (R_2 is an alkyl group having 1 to 2 carbon atoms or a halogenated alkyl group, a halogenated alkyl group having 6 to 30 carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group) an aryl group, an aryl group having 6 to 30 carbon atoms substituted with a group containing a silicon atom, or an aryl group having 6 to 30 carbon atoms), a nitro group, a group containing a silicon atom, or R
_3 (R_3 is hydrogen, hydroxyl group, carboxyl group, halogen, nitro group, amino group, cyano group, carbon number 1 to 6
an alkyl group or a halogenated alkyl group, or an aryl group having 6 to 30 carbon atoms, or a group containing a silicon atom)
Represents a substituent containing a heterocycle substituted with] (2) Using a photocurable laminate comprising a support and a photocurable layer containing as an essential component a compound containing a repeating structural unit represented by the following structural formulas [A] and [B] as an image forming material, 1. An image forming method comprising performing image forming exposure with high energy rays, and then dissolving or dispersing and removing the unexposed portions of the photocurable layer with a developing liquid to form an image on a support. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[B] [However, in the formula [A], R_0 represents a vinyl group, epoxy group, or episulfide group, and R_1 represents a Represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen. Moreover, R_1 and R_0 are substituted at either the ortho, meta, or para position with respect to the carbon atom of the main chain. [B] In the formula, W, X, Y and Z are each hydrogen, halogen, cyano group, alkyl group having 1 to 6 carbon atoms, and 1 carbon number.
a halogenated alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms substituted by an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 30 carbon atoms substituted by a group containing a silicon atom; group, aryl group having 6 to 30 carbon atoms, -COOR_
2, -COR_2, -O-COR_2 (R_2 is an alkyl group having 1 to 12 carbon atoms or a halogenated alkyl group, an aryl having 6 to 30 carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group) group, a aryl group having 6 to 30 carbon atoms substituted with a group containing a silicon atom, or an aryl group having 6 to 30 carbon atoms), a nitro group, a group containing a silicon atom, or
R_3 (R_3 includes hydrogen, a hydroxyl group, a carboxyl group, a halogen, a nitro group, an amino group, a cyano group, an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 30 carbon atoms, and a silicon atom) Represents a substituent containing a heterocycle substituted with a group)]