JPS5945440A - Thick film fine pattern - Google Patents

Abstract

PURPOSE:To enable use for electronic parts, etc. wanted to have high functions and small size, by forming a thick film pattern having an almost rectangular and high section as compared with its width and made of a photohardened photopolymerizable compsn. on a substrate. CONSTITUTION:A thick film fine pattern 4 is formed on the surface of a substrate by laminating a photopolymerizable material layer 5 and a transparent image carrier 6 serviceable as a mask having a necessary pattern on a supporting substrate 3, exposing it to active rays 7 from the side of the carrier 6, and removing the unexposed parts of the carrier 6 and the layer 5 by spraying a developing soln. 8. The pattern 4 is formed by this method so as to give an almost rectangular section having >=20mum height relief, 5-200mum width, >=10mum distance from an adjacent relief pattern, and <=1/1.5 ratio of said width to height.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on subsection 1. Recoil, high-density single connector, high-density wiring, etc. Each tili T(-(, microscopic, high precision, high density black Yu thick one-change pattern used for child parts, history details are 20 ti in height. With the above, the cross-sectional shape is y rectangle J
[The width should be 5 to 200μ, the distance between adjacent patterns should be 10zt or more, and the ratio of Ill to height should be 1 to F or less. lr sign) +, 5+
It is related to film fine patterns.

There is a limit to the thickness of fine patterns using conventional photoresist or screen printing technology, and as shown in Figure 1 (the height of fine pattern 2 formed on substrate 11 is 51+) 1 [] /I or less,
There is also a 1,1 film resist where V is 3 (] ~ 5 [, I ft), but in this case, υ'r is the cross section of pattern 2 = If of the L method] a and the height of 11 no. 11; is 1/1 is 11 moxibustion small, and ノ[(+usually is pattern 2σ month 11 a
1/Cyst membrane]: 1. <Equivalent to pattern height h)
It was below. Historically, the plate phase IJ-F pattern 2' for letterpress printing has a Fuji-shaped cross-sectional shape to prevent deformation when force is applied during printing, as shown in Figure 2.
In this case, the distance between adjacent patterns was close at the bottom. Therefore, these conventional patterns are relief [
1), it is difficult to obtain a thick film fine pattern with a high relief height and a rectangular cross-sectional shape, so high performance and miniaturization are required. There was a drawback that it could not be used.

The present invention is a completely new technology developed in view of the drawbacks of the conventional technology.
This relates to a thick film fine pattern in which the i-shaped plane is &gl, r') and the ti-shaped plane is tJ1.

In order to obtain the above-mentioned thick film fine pattern, the present invention uses a photosensitive resin composition that causes a photoreaction by irradiation with actinic rays, and is photocured to change from a liquid state to a solid state. W has the property of reducing solubility against rough cutting;-
Use the tlj match silk composition 1d2. Among this type of photosensitive resin compositions, it is well used as a photoresist.
"C divalent composition, diazo yarn composition, light: 11 [Soluble compositions, etc. must be used to harden thick films." It is used for the purpose of ``ill''.

In addition, in the present invention, a static hardening composition was used instead of a solid photocurable composition.
Moon III mountain is solid) Y, hardening 1'1 hesitation 11II! 4 things, (; various solutions to remove C111 town 1111 minutes?
In order to remove the unhardened H'Hji in M I'+'i' at 111, the relief pattern is not yet cleared by various types of cutting. Chemical 11
In contrast, the liquid photocurable composition JJy used in the present invention simply washes away the uncured material and Depending on the situation, air blow, shower, etc. 41! This is because it has a 7t-1j feature that can be removed even by mechanical means and allows a relief pattern with clear L and C contours to be obtained.

) As a specific example of Yshikogogumi sakamono (↑, the following is as follows).

JJIJ, used in the present invention) 'r; Polymerizable polymer composition that utilizes the yL combination of the unf1181 phase group,
1 each, such as those that utilize ring-opening polymerization of "Ogisilane"(;
′Φ is a force, and a representative example is ethylenic nonfr: pre-T1 that makes 5 phase groups 11? Rimmer and Ejiren depending on need? 'I, (111 ~ body in saturation,) Y polymerization initiation C 1 [, it, % polymerization inhibition II - cutting is 1 bu, [A] Vessel 1 omo ℃. "Double blur 7 bilimers include unsaturated polyurethane, unsaturated II soleurethane, polyester acrylates, unsaturated polyamine I, unsaturated, lr liimide, and unsaturated 71? riether, unsaturated poly(meth)acrylate and each of these extractants, carbon-
Illustrative examples include compounds containing carbon double bonds. It is common to use these pre++2 limmer 0 number average molecular knees having a molecular weight of substantially 500 or more.

Furthermore, 1.6 specific examples are unsaturated, l? I.J.
For Nisder and alkyd, for example, maleic acid,
Unsaturated fumaric acid, itaconic acid, etc. are acid anhydrides and ethylene glycol, nolopylene glycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, pentaerylene glycol (
Lit, I-rui with terminal hydroxyl group, 4y+? Polyesters with polyhydric alcohols such as lysotadiene, hydrogenated or non-hydrogenated 1,2-polycitadiene-acrylonitrile copolymer, succinic acid, adipic acid, phthalic acid, isophthalic acid, phthalic anhydride, which are some of the acid components, trimerit ff
11. C Polyesters whose i value has been changed to any saturated polybasic acid, or polyesters modified with dry fig oil fatty acids or semi-dry oil fatty acids, etc., are unsaturated polyurethanes, that is, 2 or more terminal hydroxyl groups. fjsu4 +l
? l Oril and 71? Products in which a compoundable unsaturated group is introduced using the terminal incyanate group or hydroxyl group of a compound linked via a urethane group derived from isocyanate, such as the above-mentioned multiple curved alcohol, 7
1? 1+ such as Liesdel polyol and polyneedle polyol? 1,4-polybutadiene with lyol-terminated hydroxyl groups, hydrogenated or non-hydrogenated 1,2-d? Liptadiene, citadiene-styrene copolymer (combination), butadiene-acrylonitrile copolymer and polyisocyanate such as toluylene diisocyanate, diphenylmethane-4,4'-diincyanate, and di-1'-diisocyanate 1/Using the reaction I11 of the terminal isocyanate or hydroxyl group of tan (2) unsaturated group introduced, 1, 1), the above 17 unsaturated carboxylic acid or 1) Hydroxyl, callus, 7mino #-7, C etc. In the reaction between a compound having active water 2 and incyanate, an unsaturated group is introduced or a carboyacyl group is introduced. A compound in which an molecule (10T) is introduced by reaction with a hydroxyl group, or a compound in which the above-mentioned unsaturated and 1-dicarbonate molecules are linked with a polyiso7anate. That is, acrylic acid or methacrylic acid is made to coexist in an ester reaction system of polybasic acid and polyhydric alcohol, and the molar ratio of each is adjusted to co-condensate to give a molecular weight of about 200 to 5000 1W, such as adipine. Acrylic in the ester reaction system between acid, phthalic acid, isophthalic acid, or acid anhydride, and polyhydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerin, trimedylolpropane, and pentaerythritol. Condensation products in the coexistence of acid or methacrylic acid, epoxy acrylates, such as polyhydric alcohols, polyhydric phenols, or compounds with epoxy groups that leak out due to the polycondensation reaction of polyphenols with epichlorohydrin or alkylene oxybi. Esters with acrylic acid or methacrylic acid, nf-combinable carbon-carbon di-11 added to the side chain
[Polymer compound having a bond, example t Hough 1? Compounds obtained by reacting polymeric compounds with hydroxyl groups such as ribinyl alcohol and cellulose with unsaturated carboxylic acid or C1 anhydride, and polymers of acrylic acid 7l, - is methacrylic acid. Or like a copolymer1. c A polymer compound with a carboxyl group with an unsaturated alcohol, glycidyl acrylate or methacrylate bonded to Nisder, a combination of 1L (71/co-v containing 1 inic acid) and allyl alcohol, hydroxyalkyl acrylate size f, reaction products with Zk main methacrylate [/-], glycidyl acrylate or ('; can be mentioned.

In addition, various compounds include +I11,4 polynotadiene, 1.2-71? Lysotadiene, butadiene
Styrene copolymerization, sitadiene-acrylonitrile copolymer, hydrogenated product between PDM, +11.1, l-, invbray isobrene copolymer, ethylene propylene copolymer, +2 Examples include unsaturated modified imes in which ethylenically unsaturated groups are introduced into compounds on various rubbers shown in Il using known techniques.
[Compound 1 can be used as it is, but if the unsaturated group is
Tire.

It is convenient to use a compound. Furthermore, in the case of a rubber compound containing 41 1,2-polybutadiene segments, a nuclear phase group can be easily introduced by adding maleic anhydride to the compound.

As prepolymers other than -I-, by a mechanism other than the addition of an edylenic triadic bond) Y; a compound that does not contain the double bond that polymerizes, for example, water + iJ fg-type nylon polyvinyl alcohol and its derivatives tf; Even if I use my body, I can't change anything at all.

Various known compounds can be conveniently used as the monounsaturated phase of ebulene+'1-unsaturated phase, and examples of such compounds include unsaturated carboxylic acid such as acrylate and methacrylic acid. ? :): or its Nisdel, such as alkyl, cycloalkyl, halogenated alhyl,
Alkoxyalgyl-, human-90xy-alkyl-, aminoalkyl-, cut-dihydronol-7-lyl, allyl-, glycidyl-, benzyl-, phenol-sheet-crystalline 1-1, and methacrylate, alkylene glycol, poly, oxyalkylene glycol- Nofake diacrylate and methacrylate, trimedylolpropane triacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate, etc., acrylamide, methacrylamide or its 5
N in force conductors, e.g. alkyl, hydroxyargyl
lie I9! ! &: L, N, N'-substituted acrylamide and methacrylamide 8, diacetone acrylamide 1 and methacrylamide 9, N, N'
-Alkylene bisacrylamide 8 and methacrylamide 1. (and allyl compound's proboscis, such as allyl alcohol, allyl isocyanate, diallyl phthalate, triaryl cyan[/-t/, [and, maleic acid, no/J'
C71 main acid, fumaric acid (sodium nitride, such as argyl, argyl halide, alkoxyargyl mono!!: or sima 1/ate and fumarate, (
and other unsaturated phase compounds ebastyrene, vinyltoluene, divinylbenzene, N-vinylcarbazole, N
-Hinylpyrrolidone/, (name 4) can 2)
. 3) Part of these j) 4M isomers.
-] Phenylene bisazide 4,4'-diazide, benzophenone, 4,4'-diazide, gonylmethane, 4,4'-diazide, 2,6-di(4'-
diazide 9benzal)-cycloh8-linone, /1,4
'-diazide stilbene-[Y-/J n, -hon,
47+ly, 4,4/-to diazi1, difenino, 4,4'-diazidostilbene-2,2'-sodium disulfonate, etc. to l+'1. You can change your mind.

Konera's +p, l 1st holiday is against Pre-11 Sorima-100 Tsuyo Club, 〇-:' OOiT! :;” It is good without addition in the + part σ2 range.

When the light market is started, various known photosensitizers can be used.

The polymerization initiator should be in the excitation wavelength range) A relatively small 11S absorption at °C7. Relief patterns that are several times the height of Ill are also produced by JJy.

This 'J7':C)Y; The molar extinction coefficient ε of the polymerization initiator is 1.5 in the region around the excitation wave t, and is preferably 1000 r or more, particularly 1 to 700/! / moe cm range is 5 chairs.

An example of such Y and negotiation start bar 1j is shown by the following equation.

■(1 It, -C-C-R2 11 OR1 It + phenyl group or li? (substituted phenyl group, T?,
, :11-1+ hydroxyl group, alkoxy group, halogen, [N:(: 7K
(k'l J-1=, alkoxy-based benzoyl, benzoin methyl needle, benzine ethyl ether, benzoin zolobyl ether, benzoin isozolobyl needle, penzoin bupuri 1-
Ether, penzoin isopdi A/conyl, 7,
2-shihi l-'r+kishi 2 phenirashi tofu 1 non,
2.2-dimethoxy-2-phenyla-tophenone,
2.2-jethoxy-2-phenylaceto-phenone,
1. D: For the composition, D, D C]
1-10 IRI? C can be used within the range of t qb.
Colander.

Thermal polymerization′! Apricot+l-/i'l Toshi' [Hydrogynone, mono 2L ball] Boulhydride-diphenyl-P-penzoginone, picric acid, SiI)
Examples include -fluorophenyl'1mine, (2)-methoxynoenol, and 2,6-di-tert-glutyl-P-cresol 7C. If you cut these heat fft restrictions by 1,
It is desirable to prevent thermal titration reactions (IIA reactions). Therefore, heat sintering inhibition 11-addition of shaving 1) 1 is 1. / +l'' IJ mother - total difference with cross-linking agent [11 to 2, 0.005 to 51 (1 liter of mouth-biting old man) Q (preferably).

'J' PC Book Q Mei's II; l giant] - r in pattern shape and 71 method (upper and next, curve. That is, 2J!
As shown in FIG. 3, a fine pattern 4 (J, 1j1,
t, 1'] Sat-(IC Masashik(Sat 35zIJ So 1-
), Illa is 5 to 200 μ (preferably 10 to 1 O
Ozl), III Ratio of a to +1-ras h a/h
is 1/1. 5 or less (preferably % or less), and the cross-sectional shape of pattern 4 is r, lj-1 shape is f1, A regular curve and no. (The angle θ of the plate 6 is 90° ± 10” (
8 [D'・~100°), 1 in history? ．． The phase t7 interval 1) of the one-piece pattern 4 is 10μ or more).

In addition, if the nfl self-point support substrate 6I is used, a film or sheet-like one is used, and 4') I'141
As for each 4IIf plus books, sheets, ]1゛i-layer version, metal-i or metal,)↓c (both,
1 piece, Hiramic board, 1118 of the complex of accommodations (+f″c PI: fl,, At/,;
,, 薯゛１体斗'A''4 etc. can also be used].1
3tl 11j;σ)
Le, Sten 17, Su, God 4, ゛I Luminium, 6 Easy,
Illj IJ I1, Magon Uno, Yi's Sen alloy plate, etc. are used, but the derivation 4'1, 1 divination) 1 anti-θ no l Pi'' person.1. In case Q′1 aluminum, te;!!+ + 'l11
．． 6ii Tongue is a lantern. This (IT material 1, base 44 is ・1〆・various surface treatments J11, for example, (
A-, 汀1, etsurang, iσ [Ma, 21; 1ζ1α
In addition to processing, it can also be used after painting, steaming, etc.
I am capable.

Continuing, the process 1] e1 of the method for forming a fine pattern of a film of the present invention will be explained as follows;

When fabricating the thick film fine pattern of the present invention, grt 4 (711, 1 to (El or (A
)' to (Ill), transparent images 411, 6, etc., which will serve as masks having the above-mentioned supporting substrate 5, optical jrE combination composition 5, and pattern 4, were layered in the following order. Ik
, this 41'' active from the body 6 side) Y; irradiating the gland 7 and 1.
・F, circle,' then expose the carrier 6 and the non-exposed part of the photo JR polymerizable composition (f, blow 8; 1 digit is removed. Therefore, 011 θ11 < supporting substrate A thick film fine pattern 4 can be r/ff formed on the surface of 6. In the figure, 9 is a transparent plastic film interposed between J (-, polymerizable composition 5, etc.) [1 body 6]. It is.

1) 11-mentioned support board,) Y door II 1 synthetic silk IJZ material (hereinafter simply referred to as composition 'proboscis' and transparent painting 1!3:413
If you open your body to the door, you can use it as a way to move your body and support it immediately i)r.
M-I:, ! 'C1,n/J brother ri na wo no 9 mi ga 2
0-2. [Coating on JO()μ or coating made of the composition
After transferring the j1λ layer, t~bright image i11 bodies, for example, silver j
λL (mask by ψ, chrome mask, active 1')"C
The plastic material, which is substantially +4 bright to the line, is made of sheet 1. Printing the original pattern on glass sheets, cellophane, etc.
Layer 1 part of the composition on top of the composition.

・Or, this is lJ! At L, apply the composition layer to the transparent image layer TP41 No lj i7 Aj l knee (1')
t-, f-holding board m attachment device f! i L Temo well, furthermore, So I! ? Substrate and transparent image f'! Using Kawakyu's body control shaley, set a certain gap and place it.
15 in this gap. The composition may also be injected. When irradiated with actinic light, such as arc lamps, mercury lamps, gysenon lamps, ultraviolet fluorescent lamps, sunlight, incandescent lamps, laser lights, and LErs, the composition and transparent image may be It is preferable to arrange the dots in close contact with each other.
12 Lipropylene film, polycarbonate film A
, zlY , zlY , zlY , , zlY , , zlY , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , acetyl , 14 , polyvinyl alcohol , , cellophane , etc. . Since it has the effect of preventing adhesion with the layer T], it has an effect of 1'+).

：Yb、：、For surface encyclopedia formation After removing the image carrier, place the plate with the polymerizable composition side up (till) and attach it to a cyrano plate or a daughter plate at 1+V, and spray the developing solution onto the plate surface for an unexposed second. Method 1: Dip a brush into the developing solution and use this brush to clean the area.
(This can be done by removing one part.

The cross-sectional shape of the relief pattern is achieved by adjusting the irradiation time of actinic light. This business club +'lt
) Y; gland 1j clam: L 1iil note] 01 (・thing is 92 in 7 but not necessarily limited to. Exposure [(: The adjustment between 1 is the same pattern Ill
Test 1.1'H with a test mask with Y4, the Jj method is 11.) and Ij (+: true).

S/、Cwa? , if the release pattern is on base 1, the exposure time is reduced, 11'/! The f shape is also l7. < is increased if ivT royal angle C) t-i).

The fine pattern and supplies are as follows. ,). That is, a conductor such as copper, metal, nickel, or tin is formed in the gap between the so-called leaf pattern phases LL other than the relief pattern portion by means such as electroplating. 2
Examples of conductive patterns include small coils, high density connectors, j1'! i Will! It can be used as J, P, -. Also, different from the above example, in the case where a single resistor is constructed by embedding plating, paste, etc. in the gap between the relief patterns, it is called a fine pattern resistor and a C pattern heating element (7). It can be used.

The embodiments of the present invention will be specifically described and explained as follows.

') ζ Stream side 1 Propylene glycol, diene glycol, adipic acid, fumaric acid in a molar ratio of 0.15/0.3510.
3510. Condensation at a rate of 15 a1) is unsaturated, r?
Lee 12 sprue 47・l で'r (I'+'￥いゆα
0) 10 - 12↑X1 (, 12↑X1)
1-]I''dimethacrylic+,,----1・,ro[)n'
; μ, fγ-human: 1 ml methacrylate-1.
Part 18, benzo chloride 2 r
'11t, 4-te hundred pf-Luke de Gaulle +1. (]
Add 5 translations and create it again>Y;
S noain tai tān i - Kaku UJ father shipuko.

i%;Ql(1ql(50/1. ,, -4 to U? Light 1
ll (7[1t'pitch air 1 air circuit pattern pattern'
74 "-4-ru negative film on glass 4t, J, ,
It Ii this one died 1, part 1- IIJlsa 9 I
71 Zelizorobirennoilm 苓・)・Light A" (P1 Baii) , then add 8l'=S'l+''1 of I'-no 50μ to j ma 3
Sa70/(0a
1. Ninora then exposed negative film 41111 to 3KW 7 for 120 seconds using a cold ultra-high pressure mercury lamp. After exposure
Peel off the RISO-U VILENFILNO and wash away the unexposed and uncured areas with a 1% aqueous solution of sodium porate at a liquid temperature of 45''C.
A thick film fine pattern with relief in the shape of a pitched electric circuit was created, and then Virolin 1
Using an lf12 copper plating solution, an Al foil was used as a cathode, and an aC current density of 5 A/dm was formed in the gap between the relief patterns. After that, DuPont's polyimide film "Kashiton" (film thickness 25 μm) was used.
After drying the Bostic phenolic resin-nitrile rubber adhesive rXA564-4 on top of the film IC? , is 5 tt
Soil 8 [2 electric 'j'! Heat the F-plated item with aluminum foil at 150℃ for 60 minutes.
Then, remove the 5-layer foil with aqueous solution of sodium filtrate and remove the foil to give a density of 18:1 [1 piece/nun, conductor)'G'70 tt, ITE.
70 Il, cylindrical spacing 301t r/) Jl/l electrical membrane circuit a).

Example 2 2,2-dimethoxy-2-feJ-acetonephenone was used as a substitute for the L, TIk-related composition of Example 1, Nzoin isobutyl ether, and polymerized to l:=')'. flH Silk IJy, 'Using the proboscis' [, 4・ηlx,) 4111^' Creating a stone air circuit 1. Ta.

Actually, 11 examples are used for the negative film on the flow side 1, and the rl+ of the transparent part is
In place of a negative film having a spiral pattern of 20 μm and IIJ in the opaque area of 80 μm, 2) Y; A fine coil with a spiral pattern of conductor 1180μ, conductor spacing 20μ, and conductor film 19.60μ was created.

Example 4 In Example 1, the 70 tt subere was replaced with a 150μ subere, and the light T By the same operation except that the light time was 540 seconds, Ill 30 μ, height 150 tr,
A relief shaped like an electric circuit with a pitch of 70μ is 1'J.
Two thick film patterns were created. (At this time, the angle between the side surface and the supporting substrate was 92'.) Using this pattern, 1. c condition”,
A thick film electric circuit was created by etching away the aluminum foil, which was then heavily coated with copper.

υζζExample 51Series 17inadibate (diol, molecule 142
．． 00 C) ) 2 fl Tolylene diisocyanate filter 5 RIX, zigdyl tin lauray) 0.5 in rJ part
1 part was processed and reacted at 70"C for 2 hours. Then, to this was added Evurene Kari Palm L-', propylene oxide copolymer (Ejilene) KINTRO 5 wt 'L'+ Kaiboshi J, Glock Jl; '+TIf book Jimer, molecule)
rt 2.0 []O) I D 0 parts were added and reacted to form a block copolymer having incyanate groups at both ends.
1 to α-H-l-”17x, I:1-l-methacrylate
Part I-25, Hyde 50 Guinon (] 11 minutes, 70”
A polymer was prepared by reacting with C for 2 hours.

To this polymer 30 [month'W1], (χ-human 20 xyzolobyl methacrylate t/-to Zs part, α-ethylhexyl acrylate 151 ff A nine-polymerizable composition was prepared (7). This composition (it is a starch syrup-like composition).

Is this #1 polymerizable composition? Apply 100μ thick aluminum to a thin plate with a thickness of 150μ, and apply 9tt/'nosano・) to a thin plate. (1) Place the glass plate on the l- with lightning and air patterns of 50 μp in the transparent part and 100 μp in the non-transparent part. Then, the light used in Example 1 was exposed for 240 seconds at 11<%. After heating, the polypropylene film was peeled off, and the uncured parts were washed with a 1% aqueous solution of alkylbenzenesulfonic acid at a temperature of 40°C, and the aluminum thin plate was washed. HiK Ill 50μ, 11i1 interval 100
Create a pattern with a relief of 100 tt in madder using μ bits. The relief part of this pattern is outside P.
Let Ce'fn be in phase s with real Mf+ 1'/ll 1
l to ``city Noah) f I-, 1,: Leno, Aluminum), J, i-9・Hikikei 1 no stile (1, Qi country 0 Raku to f',) 7; T.

[Brief explanation of the drawing]

Figure 1 and Figure 21, ? +'l? Theory showing no future pattern, 4 times, mark, 3 +:<+ +yoA\
゛)'＾ Ura showing Akira's turn, 4 times, Figure 4 shows Akira's pattern to Wood I! Explanatory diagram showing I (u + / attack one ■ Nii'-). 1. The moon, δ 1 group I Jl!,, 2. 2',, 4 is a pattern, 5 ri 1. yC: Polymerization 1'1: Composition'proboscis,
6 cores, 7 is round wire, 8 (, January mail, tr4
'8'j,, 9Q1-]]゛rah: -Y-tsuk7,7'ifiv J--C seaweed).

Claims (1)

[Scope of Claims] From the photocured product of the photopolymerizable composition,
In a thick film fine pattern, the cross-sectional shape of the relief pattern is y/)4J type and 111 of the pattern is 5 to 5. 200 tt, and if the spacing between adjacent relief patterns is 10 tt or more, only the above +1'l and the sieve and -1 I are 1 - 100 tt or more. Ein pattern.