JPS6035930B2 - curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to curable compositions useful as dry thin film photoresists or in their preparation, and to cured insulating coatings coated onto various substrates.

The curable composition of the present invention contains, by weight, 0.5% to 98% epoxy resin, {B} 0.5 to 98% polyvinyl acetal, and {C} 0.1% to 10% aroma. contains a group onium salt, where the sum of the above ■, [B- and ■] is 100%, and 'C' is the formula '1' [
Aromatic halonium salt represented by (R)a(RI)bD]sa[MQd]-(de), formula (21)[(R)f(
Group Va aromatic onium salt represented by R2)g(R3)hE]sa[MQd]-(de), and formula [3}
[(R)j(R4)k(R5)mG]sa[MQd]-(
An aromatic onium salt of a Group Via element represented by monovalent aliphatic organic groups, R3 and R
5 is a polyvalent organic group forming a compound ring or fused ring structure with E or G, D is a halogen group, e.g. 1, E is N, P, As, S
Group Va element selected from b and Bi, G is a Group Vi element selected from S, Se and Te, M is a metal or metalloid, Q is a halogen, a is an integer of 1 or 2, b is 0 or 1
, the sum of a+b is 2 or the valence of D, f is an integer of 0 to 4, g is an integer of 0 to 2, h is an integer of 0 to 2, f+g+
The sum of h is 4 or the valence of E, j is an integer from 0 to 3, k is 0
An integer of ~2, m is an integer of 0 or 1, the sum of i + k + m is 3
Or the valence of G, c=de, e is the valence of M, 2 to 7
d is an integer greater than e and up to 8).

The groups encompassed by R may be the same or different, and a hard aromatic carbocyclic group of 6 to 2 carbon atoms is a double cyclic group,
It may be substituted with 1 to 4 monovalent groups selected from C, -8 alkoxy, C, -8 alkyl, nitro, chloro, and the like.

R is more specifically phenyl, chlorophenyl, nitrophenyl, methoxyfenyl, pyridyl and the like. R
The groups included in I are divalent groups, such as .

R2 and R4 groups include C, ~8 alkyl such as methyl, ethyl, etc., substituted alkyl such as 1C2 OC戊, 1CH2
COOC2 public, 1CH2COCH3, etc. are included.

The R3 and R5 groups include the following structures, Q' is ○, C
Z is selected from O, S and S, and R' is a monovalent group selected from hydrogen and hydrocarbon.

The metals or metalloids encompassed by M in formula 1 are transition metals such as Sb, Fe, Sn, Bi, AI, Ga, ln, T
i, Zr, Sc, V, Cr, Mn, Cs, rare elements such as lanthanides such as Cb, Pr. Nd etc., actinides such as Th, Pa, U, Np etc., and semi-metals such as B,
P, As, etc.

MQ; Tsuba anions encompassed by (de) are, for example, BFZ, PF5, AsF, SbF, FeCIZ,
SnCI, S ratio, BjCI, etc. Halonium salts encompassed by Formula 1 are for example. Group Va onium salts encompassed by Formula 2 are, for example.

Group Via onium salts encompassed by Formula 3 include, for example.

Onium salts of formulas 1-3 can be prepared in a variety of ways.

The onium salt of formula 1 can be prepared by combining the arylhalonium hydrogensulfate salt under aqueous conditions with the corresponding hexafluoric acid or salt such as YIMF.
6 (wherein YI is hydrogen, an alkali metal ion, an alkali metal ion, or a transition metal ion). In addition to the metathesis described above to prepare the corresponding halonium salts, M. C. C
J. Aserio et al. Am. Chem. S.M. 81,3
36 (1959) or M. C. Berin hoko r
J. et al. Am. Chem. S ratio. 81,342 (195
It can also be prepared by the method shown in 9).

Group Via compounds such as sulfonium, selenonium and telluronium compounds are described in J. W. KMpczyk and W. E. McEwen, J. Am. Chem. Soc.
, 91145 (1969), A. L. Maycock and G. A. Berchtold, J. 0rg. Chem
．． , 35M. 8, 2532 (1970), Sun. M. Pi
No. 2,807,648 to E.T.T. Gbetha
ls and P. Mt. B of De Ra Etzky. S.M. C
Him. &1g. , 73 Pay 6 (1964), Sun. M. skin; chester and F. W. J. of Moribukuro trom. A
m, Chem. S blood,. 513587 (1929) and the like. Methods that can be used to produce Group Va onium salts, such as arsonium, antimonium and bismasonium, are described in the MethMen der and Scale Nishen Chimie
ll/2, 591-640 (1985) and K. Sas
se, idid, 12/1 79-112 (1963)
It can be seen in

The term “
"Epoxy resin" includes any monomeric, dimeric, oligomeric or polymeric epoxy material containing one or more epoxy functional groups.

For example, those resulting from the reaction of bisphenol-A (4,4'-isopropylidenediphenol) with epichlorohydrin or the reaction of low molecular weight phenol-formaldehyde resins (/borac resins) with epichlorohydrin. These resins can be used alone or in combination with epoxy-containing compounds as reactive diluents. Diluents such as phenylglycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, and allyl glycidyl ether can be added as viscosity modifiers. . Additionally, the scope of these compounds can be extended to include polymeric materials containing terminal or pendant eboxy groups.

Examples of these compounds are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the comonomers. Other classes of epoxy-containing polymers that are subject to curing using the above catalysts include epoxy siloxane resins,
Epoxy polyurethane and epoxy polyester. These polymers typically have epoxy functionality at the end of the polymer chain. Epoxysiloxane resin and its manufacturing method are described by E. P. Plueddemann and G.
Fran Hokor's J. Am. Chem. S.M. 80632
5 (1959). As described in the literature, epoxy resins can also be modified by a number of standard methods, such as reaction with amines, carboxylic acids, thiols, phenols, alcohols, etc., as described for example in U.S. Pat.
No. 0, No. 3369055, No. 3379653, No. 3
No. 398211, No. 3403199, No. 356385
No. 3567797, No. 3677995, etc.

Further examples of epoxy resins that can be used are Encyclope
Dia of Polymer Science
andTechnology, Vol. 6,
1967, InterReclencePlish
e is shown in New York, pp 209,271. The polyvinyl acetal that can be used in the curable compositions of the present invention can be, for example, a mixture of units chemically combined with R6
is selected from hydrogen, C, ~8 alkyl, such as methyl, ethyl, butyl and mixtures thereof.

Polyvinyl acetals that can be used in the practice of this invention are further described in the Encyclopedia of PolymerSci
enceand Technology, Japan. F.
Mark and N. G. Gaylord, Vol.
．． 14, 149 (1971). The curable composition of the present invention can be cast from an organic solvent solution into a dry thin film photoresist. Suitable organic solvents that can be used include, for example, methylene chloride, chloroform, methyl ethyl ketone, cellosol acetate, tetrahydrofuran, acetonitrile, etc., in an amount of from 1 to 8% by weight of the curable composition.
used in This curable composition can be thermally cured at a temperature of 100 to 200 qC. Preferably, the curable composition of the present invention can be exposed to ultraviolet light to form a cast thin film in a solvent-resistant state.

When used as a dry thin film photoresist, wavelength 18
49A~4000△ and strength at least 5000~800
00AW/By irradiating the surface with ultraviolet rays, a pattern can be created on a thin film using a mask. The lamp systems used for the generation of such radiation include ultraviolet lamps, e.g. formed by individuals. The lamp has a wavelength of approximately 1849A to 4000A, preferably 2400A to
It can include a jacket that can transmit 4000Δ light. The lamp envelope can be made of quartz, such as Spectrocjl or Pex. Typical lamps that can be used to provide ultraviolet radiation include, for example, medium pressure mercury arc lamps such as the GEHT37 arc lamp and the Nova450
It is a W arc light. Curing can be effected by a variety of lamp combinations, all or part of which can be operated in an inert atmosphere. For curing of dry thin film photoresists using ultraviolet lamps, the radiation beam on the substrate may be at least 0.01 watts per square inch.
The curable composition may contain inert ingredients such as inorganic fillers, dyes, pigments, bulking agents, viscosity control agents, processing aids, ultraviolet light shielding agents, etc. in amounts up to 100 parts per 10 parts of epoxy resin. good.

Curable compositions can be used for metals, rubber, plastics, molded parts,
It can be applied to substrates such as thin films, paper, wood, glass, cloth, concrete, ceramics, etc. Examples are shown below to facilitate implementation of the present invention, but these examples are merely illustrative and do not have a limiting meaning.

All parts are parts by weight. Example 1 Vorivinyl formal (Mo ship anto Fo dish var12/85) lo part, Ciba-Gigy
A solution consisting of 2.5 parts of Araldite ECN 1299 cresol novolacepoxy resin, 0.3 parts of triphenylsulfonium hexafluoroantimonate, and about 80 parts of chloroform was cast onto a glass plate into a 5 mil thin film.

Peel off this thin film and place it at a distance of 6 inches.
Exposure to ultraviolet light from an HT37 medium pressure mercury arc lamp was performed for 3 minutes through a glass contact mask. After irradiation, a visible image was observed in the thin film. The film was immersed in chloroform to develop the latent image. A negative image of the mask clearly raised in the thin film was produced. Example 2 A solution prepared from Formvar 15/9 polyvinyl formal, 5 parts of the epoxy resin (ECN1299) of Example 1, 0.3 parts of triphenylsulfonium hexafluoroantimonate, and 8 parts of methylene chloride was added to a polyethylene terephthalate base. It was cast as a 5 mil thin film on top.

A contact mask was then placed on top of the resulting composite and exposed to UV light for 3 minutes as described in Example 1. The composite thus obtained was then immersed in 2-ethoxyshetylacetate and developed. A polyethylene terephthalate substrate was thus obtained with a negative image of the mask on its surface, which was useful as a printing plate. Example 3
Fo dish var15/9 insect 1 part, triphenylsulfonium hexafluoroarsenate 0.3 part, ~aidi
A curable composition was prepared by dissolving 5 parts of teECN1299 and about 80 parts of methylene chloride.

The resulting solution was then cast onto a glass plate. When the solvent was evaporated from this solution, a translucent thin film was obtained. This thin film was then peeled off from the glass substrate and brought into contact with a mask. This thin film was then deposited as described in Example 1 to approximately 1.5
Irradiated for minutes. This thin film was then heated to 100 oz in a furnace.
Heated for minutes. Developing the thin film using chloroform reproduced the clear negative of the mask. Example 4 10 parts of reaction product of polyvinyl alcohol and butyraldehyde (Butvar B-74), ~aidit
A thin film was cast onto a glass slope from a curable composition consisting of 2.5 parts of eECN1299, 0.3 parts of triphenylsulfonium hexafluoroarsenate, and about 9 parts of methylene chloride.

This thin film was peeled off from the glass plate and then laminated onto a copper-coated epoxy glass circuit slope under pressure of 130 oo. The laminate was exposed to ultraviolet light using a contact mask as in Example 1. The laminate was then developed using chloroform to produce a negative image of the curable resin on the copper. The copper laminate was then etched using ferric chloride. A copper coated laminate was obtained with a positive image of the mask in the copper on the surface of the epoxy glass substrate. Example 5 Dayglo T-
A curable composition was prepared as described in Example 4, except that 0.1 part of No. 13 pigment was used.

A thin film was molded onto a polyethylene terephthalate thin plate. After drying the film, it was covered with a contact mask and exposed to ultraviolet light as described in Example 1. The thus irradiated photosensitive thin film-polyethylene terephthalate composite was then brought into contact with a flat white paper and heated under pressure to 13,000 ℃. A clear negative image of the mask was obtained on white paper. It was found that this composite could be used to transfer clear negative images of the mask onto several additional sheets of paper using the same procedure. Based on the above results, the curable compositions of the present invention can be used as dry thin film photoresists to produce printing plates, copper-coated laminates, etc.

The following example illustrates the use of diarylhalonium salts with certain organic dyes as visible light photoinitiators for epoxy resins.

Example 6 Formvar15/9 group 10 copies, ~aiditeEC
2.5 parts of N1299, 0.3 part of diphenyliodonium hexafluoroarsenate, 0.1 part of benzoflavin
A methylene chloride solution consisting of approximately 80 parts and 80 parts of methylene chloride was cast onto the Mylar film.

After drying the film, it was subjected to imagewise exposure using a visible light source, a GE375W photographic bulb. A clear image was formed in the thin film after 5 minutes of irradiation.

The latent image was developed using chloroform, 2-ethoxyshetylacetate or methylene chloride, resulting in a sharp raised replica of the mask. The above steps were repeated, except substituting acridine olethochloride for penzoflavin.

Additionally, a third film was made using phosphene-R dye in place of benzoflavin. Substantially equivalent results were obtained with each of the dyes used in place of penzoflavin. A curable composition was prepared as described above, replacing the Fo dish var 15/9 spots with an equal amount of ethyl cellulose.

Thin films were molded from this mixture and subjected to imagewise exposure using a contact mask. When an attempt was made to develop this thin film, the exposed thin film was completely dissolved in chloroform. This indicates that crosslinking did not occur in the absence of the polyvinyl acetal required to make the dry thin film photoresist. In addition to the above-mentioned dyes used in the visible light curable compositions of the present invention, other dyes that can be used with diphenylodrium salts in the practice of the present invention include, for example, Kir
k-○thmer Encyclopedia, sec
ond edition 965, Vol. 20pp
l94-7, John Wiley & Sons, Ne
A cationic dye as shown in wYork.

In addition to the cationic dyes mentioned above, basic dyes can also be used;
For this, see Kirk-CMhmerEncy above.
clopedia, Vol. 7, pp. 532-4. Some examples of cationic dyes that can be used include acridine orange C.I. 1.460
05 Acridine Yellow C. 1.460
25 Setoflavin T, C. 1.490
There is 05.

Furthermore, some examples of basic dyes that can be used include:
Hematoporphyrin 4,4'-bisdimethylaminobenzophenone, 4,4
'-bisdiethylaminobenzophenone, etc.

Claims (1)

[Scope of Claims] 1 (A) 0.5% to 98% epoxy resin, (B)
0.5 to 98% polyvinyl acetal or (C)0
．． Contains 1% to 10% aromatic onium salt on a weight basis, where the sum of the above (A), (B) and (C) is 100%.
%, and the above (C) is the formula [(R)a(R^1)
bD]＾c_+[MQd]＾-＾(＾d＾-＾e＾), an aromatic halonium salt represented by the formula [(R)f(R^2
)g(R^3)hE]^c_+[MQd]^-^(^d
Aromatic onium salt of group Va element represented by ^-^e^) and formula [(R)j(R^4)k(R^5)mG]^
Aromatic onium salt of group VIa element represented by c_+[MQd]^-^(^d^-^e^) (where, R is a monovalent aromatic organic group, R^1 is a divalent aromatic Organic group, R^2 and R^4 are monovalent aliphatic organic groups selected from alkyl, cycloalkyl and substituted alkyl, R^3 and R^5 form a heterocycle or fused ring with E or G. A polyvalent organic group selected from aliphatic groups and aromatic groups, D is a halogen such as I, and E is a group V selected from N, P, As, Sb and Bi.
A group a element, G is a group VIa element selected from S, Se and Te, M is a metal or metalloid, Q is a halogen, a is an integer of 0 or 2, b is an integer of 0 or 1, the sum a + b is valence of 2 or D, f is an integer of 0 to 4, g is an integer of 0 to 2, h is 0
An integer of ~2, the sum f+g+h is 4 or the valence of E, j is 0
An integer of ~3, k is an integer of 0 to 2, m is an integer of 0 or 1,
The sum j + k + m is 3 or the valence of G, c = d - e, e is M
a valence of 2 to 7, and d is an integer greater than e and up to 8), and mixtures thereof. 2. The curable composition according to claim 1 in the form of an organic solvent solution. 3. The curable composition according to claim 1 in the form of a thin film. 4 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is a unit selected from various units chemically combined with ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R ^
6. The curable composition of claim 1 comprising a polyvinyl acetal consisting essentially of a mixture of about 5 to about 5,000 polyvinyl acetals (wherein 6 is a C_1_8 alkyl group). 5. The curable composition according to claim 4, wherein 5R is methyl. 5. The curable composition according to claim 4, wherein 6R is butyl. 7. The curable composition according to claim 1, wherein the aromatic onium salt is an aromatic iodonium salt. 8. The curable composition according to claim 1, wherein the aromatic onium salt is a salt of a Group Va element. 9. The curable composition according to claim 1, wherein the aromatic onium salt is a salt of a Group VIa element. 10 Claim 1 in which the aromatic onium salt is triphenylsulfonium hexafluoroantimonate
The curable composition described in . 11. The curable composition according to claim 1, wherein the aromatic onium salt is diphenyliodonium hexafluoroarsenate. 12. The curable composition according to claim 1, wherein the aromatic onium salt is triphenylsulfonium hexafluoroarsenate. 13. The curable composition according to claim 1, wherein the polyvinyl acetal is polyvinyl formal. 14. The curable composition according to claim 1, wherein the polyvinyl acetal is a reaction product of polyvinyl alcohol and butyraldehyde. 15. The curable composition of claim 1, comprising a chloroform solution of polyvinyl formal, cresol-novolac epoxy resin, and triphenylsulfonium hexafluoroantimonate. 16. The curable composition of claim 1 in the form of a methylene chloride solution containing a reaction product of polyvinyl alcohol and butyraldehyde, a cresol-novolac epoxy resin, and triphenylsulfonium hexafluoroarsenate. 17. The curable composition according to claim 15 in the form of a cast thin film. 18. The visible light curable composition according to claim 1, containing an aromatic iodonium salt and an organic dye.