WO1986007071A1 - Derives de polybutadiene contenant un groupe thiol, composition a base de resine les contenant, procede de preparation de ces derives et de cette composition a base de resine, et procede de production de cartes de circuits - Google Patents

Derives de polybutadiene contenant un groupe thiol, composition a base de resine les contenant, procede de preparation de ces derives et de cette composition a base de resine, et procede de production de cartes de circuits Download PDF

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Publication number
WO1986007071A1
WO1986007071A1 PCT/JP1985/000295 JP8500295W WO8607071A1 WO 1986007071 A1 WO1986007071 A1 WO 1986007071A1 JP 8500295 W JP8500295 W JP 8500295W WO 8607071 A1 WO8607071 A1 WO 8607071A1
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Prior art keywords
urethane
resin
reaction
compound
general formula
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PCT/JP1985/000295
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English (en)
Japanese (ja)
Inventor
Masayuki Kataoka
Yukio Yamase
Masami Yamazaki
Original Assignee
Nippon Soda Co., Ltd.
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Application filed by Nippon Soda Co., Ltd. filed Critical Nippon Soda Co., Ltd.
Priority to PCT/JP1985/000295 priority Critical patent/WO1986007071A1/fr
Publication of WO1986007071A1 publication Critical patent/WO1986007071A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/006—Rubber characterised by functional groups, e.g. telechelic diene polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
    • H05K3/4676—Single layer compositions

Definitions

  • a resin composition, the derivative, a method for producing the resin composition
  • the present invention relates to a novel thiol group-containing polybutadiene derivative, a resin composition containing the derivative, a method for producing the same, and a method for producing a circuit board using the composition.
  • the novel thiol-based polybutadiene derivative is a modified polythiol of a urethane-based unsaturated resin mainly composed of 1,2-polybutadiene, and has a free thiol group.
  • the conductor is excellent in thermosetting properties, photocuring properties, especially photosensitive properties, and the cured product has chemical resistance, especially non-decomposable plating liquid resistance, solvent resistance, heat resistance, electrical properties, etc. Is extremely excellent.
  • the radiation-curable resin composition containing the derivative is suitable for forming a metal resist film in the production of a circuit board by the additive method.
  • a method of manufacturing a circuit board by a full additive method in which a circuit is formed on a board by a resist and then a conductor circuit is formed by an electroless plating, has been known for a long time. Also, as a recently introduced method of manufacturing a circuit board, a copper layer of a copper-clad laminate is etched to form a conductor circuit, a resist film is formed leaving a through hole portion, and then an electroless film is formed. No-one tree additive There is a law (hereinafter the above two methods are simply referred to as “additive method”). The additive method simplifies each process in the production of double-sided through-hole circuit boards, compared to the so-called subtract method, which is conventionally well known as the most common method of manufacturing circuit boards. It is relatively suitable for manufacturing high-density circuit boards. Therefore, the number of companies adopting these methods tends to increase.
  • the plating conditions in the additive method are extremely severe compared to the conditions of the through-hole conduction plating used in the subtract method. For example, using a highly viscous plating solution with a pH of 12 to 13 and a plating bath in which the oxidation-reduction reaction is carried out under a high flow of 65 to 70 for as long as 10 to 20 hours Under the severe conditions to which the circuit is exposed, the circuit is formed.
  • a resist for forming a circuit pattern that is, a plating resist is required to have a performance that can withstand the plating condition.
  • the resist is used not as a temporary register but as a permanent register, the solder heat resistance and the solder heat resistance required for the solder resist used in the subtract method and the resist for the insulation protection film are required. It is necessary to satisfy the electrical and mechanical properties after heat and moisture resistance tests.
  • solder resists and resists for insulation protection coatings conventionally used in the subtract method cannot be used as the additive resist in the additive method.
  • a resist resin that satisfies the requirements of the plating resist a thermosetting epoxy resin-based electroless plating resist has conventionally been used for manufacturing circuit boards by a screen printing method.
  • the density of circuit boards has rapidly increased, and it has been required to draw a resist pattern of 100 / im level. Therefore, there is a demand for the development of a resist resin for electroless plating of a photo resist type that can form a resist pattern by a photographic method instead of the screen printing method.
  • the dry film method As a permanent photo resist, there is a dry film type resist, which is generally used for a circuit board insulating protective coating and a solder resist. However, they do not satisfy the performance of the resist method for the additive method. In addition, the dry film method has the following problems. -'
  • the formed resist pattern is likely to have a defect.
  • a photocurable resist resin composition As a photocurable resist resin composition, a polythiol is blended with a poly (en) containing urethane (meth) acrylate resin, and an unreacted diene and thiol group are obtained after curing.
  • a non-photopolymerizable resin composition is described in JP-B-53-28959.
  • a monomer and a thiol group are stoichiometrically present, and a resist is formed by an addition reaction between the amine and the thiol group.
  • Japanese Patent Application Laid-Open No. 55-27311 discloses that a mixture of an acrylic or methacrylic-terminal urethane-containing polyester and a polyester is dissolved in a water-insoluble vinyl monomer as a diluent. A radiation-curable composition containing a photopolymerization initiator is described.
  • the compound is a composition having an excess of (meth) acryloyl group, and is obtained by co-existing radical radical polymerization of (meth) acryloyl group and ene: thiol addition reaction. Improves curability in the presence of oxygen.
  • the composition uses a water-insoluble vinyl monomer as a diluent, the tack-free property of an uncured resin coating film required for a photo resist for contact exposure is insufficient. .
  • poly (ethylene glycol) and poly (propylene glycol) are poly (ethylene glycol) and poly (propylene glycol) as skeleton components of the skeleton of a (meth) acrylyl-terminated urethane-containing poridine which is a component of the composition. It is only described specifically.
  • Japanese Patent Application Laid-Open No. 55-58226 discloses, as a photopolymerizable composition suitable as a solder resist, a composition in which boritiol is blended with the same urethane (meth) acrylate resin as described above. I have.
  • the composition is substantially the same as the composition disclosed in JP-A-55-27311. Therefore, even though it can be used as a solder resist, it has tackiness and cannot be used as a photo resist for electroless plating for contact exposure.
  • the composition satisfies most of the characteristics required for an electroless plating resist in the production of a circuit board by the additive method, and the composition is used for forming a circuit board.
  • a method for producing the same was proposed in Japanese Patent Application No. 58-25613 (see JP-A-59-151495).
  • the resist film formed using the composition needs to be further improved in terms of preventing abnormal plating from breaking out. Further, there has been a demand for further improving the sensitivity at the time of exposure.
  • a photocurable resin composition suitable as a photo resist for use was obtained.
  • the composition may be easily gelled at the time of manufacture or storage, and even when gelation does not occur, the quality was unstable, such as a decrease in photosensitive characteristics.
  • the present invention has solved the problem of the resin composition, that is, a stable, electroless method of the additive method which has improved the photosensitive characteristics and the resist performance and has solved the gelation during production and storage. It is a main object of the present invention to provide a radiation-curable resin composition suitable as a photo resist for woodpeckers. Another object of the present invention is to provide a novel polybutadiene derivative which is a main component of the composition, a method for producing the same, and a method for producing a circuit board using the composition.
  • R is a divalent organic residue
  • U is a urethane bond-N-C-0-
  • X is a box having a hydroxyl group at both terminals with a number average molecular weight of 500 to 5,000, in which at least 50% of the butadiene units in the polymer are composed of 1,2-bonds. ⁇ butadiene diol reaction residue,
  • Y is a urethane-reactive residue of a polyol compound having 3 to 4 hydroxyl groups per molecule
  • Z represents a urethane-reactive residue of the diisocyanate compound, and n represents an integer of 2 to 3.
  • n an integer of 2 to 4.
  • the second aspect is a resin composition having the thiol-based polybutadiene derivative.
  • At least 60% of the resin content is the thiol group-containing polybutadiene derivative
  • the remaining resin content is represented by the following general formula:
  • X ′ represents a urethane-reactive residue of at least one diol compound selected from the group consisting of polyetherdiol, polyesterdiol and polyacryldiol having a number average molecular weight of 200 to 5,000.
  • a thiol-modified compound obtained by reacting 0.1 to 1 mol of 30 to 70% of thiol groups as free thiol groups so as to remain after the reaction with 0.1 to 1 mol of the borthiol compound represented by the general formula (2). It is a resin composition containing a thiol group-containing polybutadiidine derivative.
  • the third invention is a urethane-based unsaturated resin [A] represented by the general formula (la): 1 mol,
  • At least 60% is the urethane unsaturated resin [A] represented by the general formula (la), and the remainder is the urethane unsaturated resin [ ⁇ '] represented by the general formula (lb). 1 mole of a mixed urethane-based unsaturated resin;
  • a borthiol compound represented by the general formula (2) 0.1 to 1 mol, while blowing an oxygen-containing gas in a medium, at a temperature of 30 to 100 ° C. for 2 to 8 hours.
  • an ultraviolet curable resin composition obtained by mixing a photopolymerization initiator with the resin composition of the second aspect of the present invention is applied to a resist film by adhesion photolithography from a coating film formed by applying the composition to a substrate.
  • the thiol-based polybutadiene derivative of the first invention is represented by the following general formula (2) in an amount of 1 mol or less per 1 mol of the urethane-based unsaturated resin [A] represented by the general formula (la).
  • a novel polybutadiene derivative in which 30 to 70% of the thiol groups to which the polythiol compound [B] is bound remains as a free thiol group.
  • the free thiol group in the derivative is based on the value determined by the silver nitrate method (Industrial and Engineering Chemistry 18, No. 3161 (1946) I. olthoff et al).
  • the derivative has a hydroxyl group at both terminals having a number average molecular weight of 500 to 500.0, wherein X in the general formula (la) is composed of 1 / 2-bonds in which 50% or more of the butadiene units in the polymer chain are composed.
  • the urethane-reactive residue of polybutadienediol, that is, polybutadiene, is used as the main skeleton, and two or three (meta) acs are formed at each end via multiple urethane bonds. Either the terminal double bond of the polybutadiene chain or the double bond of the terminal (meta) acryloyl group of the urethane-based unsaturated resin [A] having a relay group. It is presumed that some of the thiol groups of the reacted thiol compound [B] were added and bonded.
  • the polybutadienediol used as a raw material of polybutadienediol having a main chain skeleton is too short if the molecular weight of the polybutadienediol used is less than 500, so that the intended effect cannot be obtained. If it exceeds, the viscosity will be too high and the workability will be reduced.
  • the fact that 50% or more of the butadiene units constituting the main chain structure of the derivative are 1 * 2-bonds indicates that the branched butyl group has strong reactivity due to intermolecular crosslinking based on excellent reactivity. It is important in forming a simple network structure.
  • the (meth) acryloyl groups at both ends are important as radiation functional groups. If the number of each (meta) acryloyl group is one, the curability of the resin due to irradiation with radiation decreases, and if it exceeds three, the properties of the cured product deteriorate.
  • the (meth) acryloyl groups at both ends are bonded to the polybutadiene chain through a plurality of urethane bonds as shown in the general formula (la). This urethane structure is indispensable for tack-free dry and uncured resin. Derivatives having one urethane structure at each end of the polybutadiene chain do not provide the tack-free properties of the uncured resin.
  • the boritithiol compound [B] represented by the general formula (2) per molecule of the urethane-based unsaturated resin [A] represented by the general formula (la) has an average of Less than one molecule, preferably 0.1 to 1 molecule, more preferably 0.15 to 0.6 molecule, wherein 30 to 70% of the thiol groups are present as free thiol groups.
  • the reaction ratio of the -polyol compound [B] to 1 mol of the urethane-based unsaturated resin [A] exceeds 1 mol, the viscosity of the derivative increases and the workability decreases. . In addition, the flexibility and adhesion of the resist film after curing, which is the final object, to the substrate are reduced. On the other hand, if the reaction molar ratio is less than 0.1 mol, the curability of the obtained derivative and the photosensitive properties as a photo resist are extremely reduced.
  • the free thiol group content is less than 30%, the curability and the photosensitive properties as a photo resist are extremely reduced.
  • the free thiol group exceeds 70%, the stability is lowered and the gel is easily formed.
  • the polythiol compound [B] represented by the general formula (2) has a molecular weight of less than 80, the product has a bad odor, and the product has the bad odor. Workability at the time of conductor production also becomes a problem.
  • a resin having a molecular weight of more than 1000 is used, only a derivative having a low viscosity can be obtained, and the sensitivity of the obtained resin to radiation decreases.
  • the sensitivity of the obtained resin to radiation decreases, and the compound having 5 or more When a resin is used, the obtained resin has poor coatability (adhesion to a substrate).
  • boron compound [B] 1 ⁇ 2-ethanedithiol, 1 • 2—pronodithiol, 1,3—pronodithiol, hexamethylenedithiol, p ⁇ nzen Examples thereof include dithiol and xylylenedithiol.
  • esterification reaction of mercaptocarboxylic acids such as thioglycolic acid, -mercaptopropionic acid, and ⁇ -mercaptopropionic acid with di- to tetravalent polyols.
  • the thiols obtained by the above method can also be used preferably.
  • Examples of the di- to tetra-valent poly * ols used in the esterification reaction include ethylene glycol, diethyl glycol, triethylene glycol, propylene glycol, dipropylene, and the like.
  • a polythiol compound obtained by opening the epoxy ring of the polyepoxy compound with hydrogen sulfide or a polythiol compound can also be used.
  • Particularly preferred polythiol compounds have low odor, curability and stability.
  • polythiol compound usually, one kind of the polythiol compound is used alone, but a mixed polythiol of two or more kinds may be used.
  • the second invention is a resin composition having the thiol-based polybutadiene derivative of the first invention described in detail as a resin component.
  • the resin composition in the resin composition, at least 60% or more of the resin content is the thiol-based polybutadiene derivative.
  • the remaining resin component is butadiene which is the main skeleton of the urethane-based unsaturated resin [A] represented by the general formula (la), which is a raw material of the thiol-based polybutadiene derivative of the first invention.
  • the thiol-based polybutadiene derivative is less than 60%, the hydrophobicity of polybutadiene is lost, and the electrical properties of the cured product are reduced.
  • the thermosetting properties after exposure and development are reduced, and the desired coating film properties cannot be obtained.
  • diol compound examples include poly (ethylene glycol) having a molecular weight of 200 to 5,000 obtained by polymerizing alkylenoxide.
  • Polyethers such as polypropylene glycol, neopentyl glycol, alkylene glycols such as 1,4-butanediol and 1 * 6xandiol, or lactones such as caprolactone Polyesterdiols obtained by ring-opening polymerization of tones in the presence of polyhydric alcohols, such as those having a molecular weight of 500 to 3,000.
  • the resin component in the composition can be cured and cross-linked by heat curing and irradiation with radiation such as ultraviolet rays, electron beams, X-rays, or a combination thereof.
  • a photopolymerization initiator and if necessary, a radical polymerization initiator, a curing accelerator, and the like are added to the composition as components other than the resin component.
  • a photopolymerization initiator and if necessary, a radical polymerization initiator, a curing accelerator, and the like are added to the composition as components other than the resin component.
  • an ultraviolet-curable composition to which a photopolymerization initiator is added.
  • Representative compounds as photopolymerization initiators for ultraviolet curing include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin acetate, benzophenone, and 2 ⁇ benzophenone.
  • benzyldimethyketal, 2.2-jetoxyphenone, 2.2-dimethyoxy-2-phenylacetophenone, benzoinisovyrobinoreethere, benzo 'Insobuchinoleethenore, 2-ethylanthraquinone and the like are preferably used.
  • These photopolymerization initiators are used alone or in combination of two or more.
  • the photopolymerization initiator is used in an amount of 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the total resin content.
  • a photopolymerization accelerator is used in combination for the purpose of accelerating curing and preventing a polymerization inhibitory action due to oxygen or the like.
  • Primary photopolymerization accelerators such as butylamine, hexamethylenediamine, diethylamine, triethylenetetramine, monoethanolamine, etc. , Jethylamine, Dimethylamine, Dimethylamine -— 'Tonoleizine, Pyridinine, ⁇ , ⁇ '-Dimethylcyclohexylamine, Dietanolamine, Triethanolamine Amins such as secondary amines or tertiary amines such as ethanolamine and mila ketone are used.
  • the composition prevents premature crosslinking during the compounding and storage of the resin.Also, the composition is capable of preventing unexposed portions caused by heat generated by the crosslinking reaction during the exposure process or transmitted to the opaque portions of the original.
  • a polymerization inhibitor stabilizer
  • Stabilizers such as di-t-butyl-p-cresol, nodroquinone monomethyl ether, pyrogallol, quinone, noidroquinone, t-butynole, and nodroquinone monobe
  • benzoquinone, methinolenoid hydroquinone, amylquinone, phenol, phenolic quinone monobutyl butyl ether, phenolic thiazine, and nitrobenzene are used.
  • additives can be uniformly dissolved in the composition or can be added in the form of a heterogeneous compound.
  • additives include various natural and synthetic polymer substances, fillers, pigments, dyes, plasticizers, viscosity modifiers, solvents, and various other auxiliaries.
  • the thiol-based polybutadiene derivative of the first and second inventions and the resin composition having the derivative are produced by the following method. (This third invention)
  • a predetermined amount of the boritiol compound [ ⁇ ] represented by the general formula (2) is dropped,
  • the desired thiol group-containing polybutadiene derivative of the first invention or the thiol group-containing polybutadiene derivative of the first invention is maintained by stirring at a selected temperature in the range of 30 to 100'c for 2 to 8 hours depending on the temperature while blowing gas.
  • a radiation-curable resin composition containing the derivative of the second invention is obtained.
  • the injection of oxygen-containing gas is extremely important, and it continues from the start of the dropping of the polythiol compound to the end of the reaction. Further, the oxygen-containing gas is blown while sufficiently stirring and mixing the reaction solution so that the oxygen-containing gas is sufficiently diffused throughout the reaction solution. If the diffusion of the oxygen-containing gas into the reaction solution is insufficient, gelation occurs at the time of dropping the boritiol compound. In particular, during high-temperature reactions (between 50 and 100), it is necessary to observe the diffusion state of oxygen-containing gas more carefully. Air is usually used as the oxygen-containing gas.
  • the reaction temperature is from 30 to 100, preferably from 50 to 80, at which temperature the reaction time is controlled in the range from 2 to 8 hours, preferably from 4 to & h, depending on the reaction temperature.
  • the reaction rate of the polythiol compound And the desired thiol group-containing polybutadiene derivative in which 30 to 70% of the thiol groups of the polythiol compound remain as free thiol groups can be obtained.
  • the reaction temperature exceeds 100, a derivative having better storage stability is obtained, but the reaction itself becomes unstable and gelation easily occurs.
  • the reaction temperature is lower than 30'c, the reaction rate is low, and it takes a long time to achieve the reaction rate of the target polythiol compound.
  • the free thiol group separation method is based on a silver nitrate method (Industrial and Engineering Chemistr 18, No. 3 161 (1946) IMKolthoff et al) in which the following formula is measured by potentiometric titration. adopt.
  • the urethane-based unsaturated resin [A] represented by the general formula (la) as a raw material is represented by the following general formula:
  • a urethane polymer [D] represented by the following general formula:
  • the diol component is at least 60% of polybutadiene diol [C] and the remainder is polyether diol [C ′], whereby the urethane unsaturated resin [A Or a urethane-based mixed resin of the urethane-based unsaturated resin [A] and the urethane-based unsaturated resin [ ⁇ ']. An unsaturated resin is obtained.
  • the number of hydroxyl groups in polybutadiene diol [C] and polyether diol [C '] should be, as a rule, 2 ⁇ per molecule, at each end of the main chain via multiple urethane bonds. It is important for binding two or three (meta) acryloyl groups. Although there may be one having one hydroxyl group in one molecule, if many hydroxyl groups are present in one molecule, the viscosity increases during the process of synthesizing the urethane-based unsaturated resin, or Gelation occurs.
  • the urethane prepolymer (D) represented by the general formula (4) is used to introduce two or three (meth) acryloyl groups at both ends of a urethane-based unsaturated resin. It is a reaction product of a polyvalent or tetravalent boryl compound and an organic diisocyanate compound.
  • trivalent or tetravalent polyol compound those having a molecular weight of 2000 or less are usually used.
  • organic diisocyanate compounds 2.4-toluene succinate, 2.6-toluene ziocyanate, 4.4'-diphenylmethane thiocyanate and xylene thiocyanate
  • Mexico-range associa- tion hexamethylene-range associa- tion, and ridge Iso cyanate
  • the urethane prepolymer [D] represented by the general formula (4) is synthesized by reacting 0.8 to 1.2 moles of an organic diisocyanate compound with respect to 1 equivalent of a hydroxyl group of a boroyl compound.
  • the reaction is carried out at a temperature of between 25 and 100 for at least 30 minutes, preferably at a temperature of between 40 and 80 for about 2 hours.
  • the reaction temperature is low, the reaction takes a long time. At reaction temperatures above 100, unduly high viscous products are obtained.
  • —As a (meth) acrylate compound [ ⁇ ] represented by the general formula (5) one molecule having one hydroxyl group in one molecule, for example, 2-hydroxyhydryl (meth) acrylate Rate, 2-hydroxypropyl (meta) acrylate, 3-butoxy2—hydroxylate mouth (meta) acrylate, 3-metoxy2 ——Hydroxypropyl (meta) acrylate, 2 ——Hydroxypentyl (meta) acrylate, etc. can be preferably used.
  • the reaction solvent is a hydrocarbon, ester, ketone, ether, halogen, which does not have active hydrogen that reacts with the isocyanate group.
  • aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic carbons such as kerosene and mineral spirits Hydrocarbons, ester grains such as ethyl acetate and butyl acetate, ethers such as methyl acetate sorbate, carbon tetrachloride, and aliphatic hydrocarbons such as 1.1,1-trichloropentane and barchlorobutylene.
  • halogenated hydrocarbons and aromatic halogenated hydrocarbons such as chlorobenzene and 0-dichlorobenzene are used.
  • urethanization catalysts such as triethylamine, triethylene diamide, and dimethyl morpholine, and tin octoate, zinc octoate, lead octoate, and naphthene
  • tertiary amines such as triethylamine, triethylene diamide, and dimethyl morpholine
  • tin octoate, zinc octoate, lead octoate and naphthene
  • Organometallic compounds such as calcium oxide, dibutyltin dilaurate, tetrabutyl1.3-diacetoxydistannoxane can be used.
  • the resin composition of the second invention described in detail above can be obtained by adding the photopolymerization initiator, and if necessary, various additives such as an extender and a reactive diluent, to thereby provide an ultraviolet-curable coating varnish. It can be used as various photopolymerization components such as a vehicle for printing inks, and by selecting and combining various additives, it is possible to obtain a cured product having desired characteristics according to the application.
  • the composition is suitably used for forming a metal resist in the production of a circuit board by an additive method.
  • a method for manufacturing a circuit board comprising: forming a resist pattern using the composition; and performing a circuit pattern measurement by an electroless plating method. Is the way.
  • the composition is directly applied to a substrate that has been subjected to a surface activation treatment for electroless plating so that the film thickness after drying becomes 10 to: LOO fim, and the solvent is volatilized. Then, a resin film is formed.
  • the composition is coated on a film-like support and dried to form a coating film. The coating film is transferred onto the substrate by a laminator or the like to form a resin film. Formation You can do it.
  • the method of applying the composition to a substrate or film is not particularly limited as long as it can apply a uniform film thickness, and the composition may be applied using a coating apparatus such as a roll coater or a curtain flow coater. Can be.
  • the ultraviolet light source is selected from a wavelength range of 200 to 500 in which the photopolymerization initiator can be activated.
  • High-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, etc. can be used as the light source.
  • the negative mask is removed, and then the non-exposed portion is removed using a solvent.
  • Various organic solvents can be used as the developing solvent. Solvents such as 1.1-trichloroethane and a mixed solvent of the solvent and alcohols are preferably used from the viewpoint of resolution and the like. Is done.
  • a circuit pattern of a resist film is formed on the substrate.
  • the resist film can be used as a corrosion-resistant film for ordinary etching, plating, and the like. Further, the resist film is irradiated with actinic rays to proceed with curing, or at a temperature of 80 to 200'c. Heat treatment for up to 120 minutes results in a resist film having more excellent properties.
  • the resist film subjected to this post-treatment includes an aromatic hydrocarbon-based solvent such as toluene, a ketone-based solvent such as methylethylketone, an alcohol-based solvent such as isobrovir alcohol, methylene dichloride, Not violated by halogenated hydrocarbon solvents such as trichlorene. In addition, it is sufficiently resistant to strongly acidic and strongly alkaline aqueous solutions.
  • the substrate on which the resist pattern is formed is immersed in an electroless plating solution, the electroless plating is performed, and a plating layer having a desired thickness is formed on a circuit portion, thereby producing a circuit board.
  • the non-west road portion covered with the resist film has no or no very little protrusion, and the precipitation is easily and easily removed. be able to.
  • the resist film formed on the circuit board has excellent electrical and mechanical properties of polybutadiene resin, and thus can be used as a permanent resist.
  • a resist film for circuit protection and a solder-resist film for solder can be further formed on the circuit board manufactured in the above steps, if desired.
  • a mixed solvent consisting of: a number-average molecular weight: 2,000, a hydroxyl value: 50 (K0H mg
  • the obtained polyisocyanate compound was a pale yellow transparent solution having a free isocyanate of 2.4 mass and a viscosity of V (20′c, bubble viscometer, the same applies hereinafter).
  • the gas to be introduced into the reaction vessel is switched to dry air and a small amount of gas is passed through it to the reaction liquid of the polysocyanate from the dropping funnel. After the completion, the reaction was continued while maintaining the temperature at 80 for 3.5 hours to obtain a residual unsaturated resin [A-1] having a residual NC0 of 0.01%.
  • sample A-1 In the synthesis of sample A-1, sample A-1 was used, except that 2-hydroxypropyl acetate; 131.1 parts was used in place of 2-hydroxyl acrylate. The reaction was carried out under the same conditions as in the synthesis of the above to obtain a urethane-based unsaturated resin [A-3] with a residual NC0 of 0.01%.
  • Example 4 In the same reaction vessel used for the synthesis of sample Al, 1 ⁇ 1 ⁇ 1 trimethylolpropane; 60 parts, mixed tri-range isocarbonate of the same specifications used for synthesis of sample A-1; 240 parts and 300 parts of n-butyl acetate were charged, and after purging with nitrogen, the mixture was gradually heated with stirring and maintained at a temperature of 80'c for 2 hours to synthesize a urethane prepolymer.
  • n-butyl acetate 249 parts, number average molecular weight: 1,500, hydroxyl value: 66.6, 91.7 of the butadiene unit of the polymer chain is a 1,2-bonded boributadienediol; 175.4 parts and number average
  • the obtained polyisocyanate compound was a pale yellow, transparent solution having a free isocyanate content of 3.8% and a viscosity of C.
  • the gas to be introduced into the reaction vessel is switched to dry air, and a small amount of gas is passed through it to the reaction solution of the polysocyanate from a dropping funnel. 115 parts of 2-hydroxylacrylate are added dropwise over 2 hours. After completion, the reaction was maintained at a temperature of 80 for another 3.5 hours to surround the reaction to obtain a mixed urethane-based unsaturated resin [ ⁇ -4] with a residual NC0 of 0.02%.
  • ⁇ -butyl acetate 340 parts, number average molecular weight: 3,000, hydroxyl group Value: 30, a polybutadienediol in which 92.1% of the butadiene units in the polymer chain are composed of 1 * 2-bonds; a solution in which 340 parts have been well dissolved in advance is added to the urethane prepolymer reaction solution in about 2 hours. After completion of the dropwise addition, the reaction was continued at a temperature of 75 for 3 hours while passing a small amount of nitrogen gas into the reaction vessel to continue the reaction, thereby synthesizing a polyisocyanate compound.
  • the obtained polyisocyanate compound was a solution having a free isocyanate content of 2.1% and a viscosity of J to K.
  • the gas to be introduced into the reaction vessel is switched to dry air, and a small amount of gas is passed through it to the reaction solution of the polysocyanate from the dropping funnel. After the completion, the reaction was continued while maintaining the temperature at 80'c for 3.5 hours to obtain a residual unsaturated resin [A-5] having a residual NC0 of 0.01%.
  • the gas introduced into the reaction vessel is switched to dry air and a small amount of gas is passed through it to the reaction solution of polyisocyanate, and 175 parts of 2-hydroxyhexyl acrylate; After completion of the dropwise addition, the reaction was continued while maintaining the temperature at 80 for 3.5 hours, to obtain a residual unsaturated resin [A-6] having a residual NC0 of 0.02%.
  • reaction vessel used for the synthesis of sample A-1 was charged with 240 parts of the same range of tri-diethylene succinate used for the synthesis of sample A-1 and 240 parts of n-butyl acetate; To 60 parts of n-butyl, add 60 parts of pre-dissolved trimethylolpropane; gradually warm and maintain at 80 ° C for 2 hours to synthesize urethane prepolymer. did.
  • n-butyl acetate 401.3 parts, number average molecular weight: 1,500, hydroxyl value: 60.2, 91.7% of the butadiene units in the polymer chain consisted of 1/2 bonds, and this double bond was converted to water.
  • the obtained polysocyanate compound was a light yellow transparent liquid having a free isocyanate content of 2.9% and a viscosity of ⁇ .
  • the nitrogen gas to be introduced into the reaction vessel was switched to dry air, and from the dropping funnel, 110 parts of 2-hydroxyshetyl acrylate was added dropwise over a period of 2 hours.
  • the reaction was continued while the temperature was further maintained for 3.5 hours to obtain a urethane-based unsaturated resin (: CA-4) having a residual NC0: 0.02% and having a free hydroxyl group.
  • the obtained polysocyanate compound was a pale yellow transparent liquid having a free isosilicate: 3.5% and a viscosity: V.
  • the obtained polyisocyanate compound was a pale yellow transparent liquid having a free isocyanate content of 4.5% and a viscosity of D.
  • the reaction vessel used for the synthesis of sample A-1 was charged with 200 parts of the same range of tri-range reagent used for the synthesis of sample A-1, and gradually heated with stirring under a nitrogen atmosphere. At a temperature of 50, 146 parts of hydroxyshethyl acrylate were added dropwise over 2 hours. Then, the reaction temperature was increased to 70'C and kept at that temperature for another 4 hours to ripen the reaction.
  • n-butyl acetate 279.8 parts, a number average molecular weight: 1,500, hydroxyl value: 66.6, and 91.7% of butadiene units in the polymer chain;
  • the well-dissolved solution was charged into a reaction vessel, and gradually heated to 50 c under a nitrogen atmosphere, and then 79.8 parts of the above-prepared hydroxyxethyl acrylate product was added dropwise over 1 hour. .
  • the reaction temperature was increased to 70, and the reaction was aged for 4 hours with stirring to obtain a urethane-based unsaturated resin [CA-7] with a residual NC0 of 0.03%.
  • Example 2 [Reaction between urethane unsaturated resin and poly'thiol compound] Ethylene glycol dimolecaptopropionate [B-1], 1.4-butanediol dimcaptopropionate [B-2] and trimethylol propylamine are used as the polythiol compound [B].
  • One of the mercaptopropionates [B-3] was reacted with the urethane-based unsaturated resin synthesized in Example 1 [ ⁇ -1 to ⁇ -6] to obtain a thiol-containing polybutadiene.
  • Various resin compositions [G-1 to G-9] having a diene derivative were produced.
  • a predetermined amount of the urethane-based unsaturated resin [A] was charged into 10 to 2000 reaction vessels, and vigorously stirred while blowing air into the reaction solution to sufficiently diffuse air into the reaction solution.
  • a predetermined amount of the boritol compound [B] is dropped therein over 1 hour, and the temperature is maintained at 50 to 80'c for 4 to 6 hours (the dropping time of the borthiol compound is maintained). Matured.
  • the free thiol group in the obtained composition was analyzed by the silver nitrate method. As a result, the free thiol group was 43 to 63% of the thiol group possessed by the reacted polythiol compound.
  • reaction temperature was changed from room temperature to 130 ⁇ (:, the reaction time was changed from 10 minutes to 10 hours, and various resin compositions [CG-1 to CG-8] were used instead of blowing air with nitrogen gas. Manufactured.
  • the synthesized resin compositions (G-1 to G-9 and CG-1 to CG-8) were stored in an incubator maintained at a temperature of 50 ° C, or stored at room temperature. The gel time was measured.
  • Table 1 shows the reaction conditions and the results of the stability test of each resin composition.
  • Urethane-based unsatisfactory Polythio-reactor can Reaction conditions ⁇ Cho stability test No. Species quantity Species quantity Quantitative ha. Bt. Time? ⁇ A temperature temperature time feeling
  • each of the resin compositions Gl to G-9 has a gelation time of 10 days or more at 50 and a stability of 1 year or more at room temperature. Is shown.
  • the urethane-based unsaturated resin [CA-1 to CA-8] synthesized as a comparative sample in Example 1 was used as a borothiol compound as described above for B-1, B-2, B-3 and 2-ethyl.
  • a (meta) acyl selected from hexyl (3-—mercaptopropionate) [B-4] and pentaerythritol tetramer-butopionate [B-5] Trimethyl phenol diacrylate as a relay monomer; 80-1.6 siloxanediol diacrylate; a mixture of 20; benzyl dimethyl ketal and a phthalocyanine compound as a photopolymerization initiator A pigment and the like were blended to prepare a UV-curable resin composition [CH-1 to CH-13] for comparison.
  • nitrile rubber-based evaporator lip 77 (Cerchilney: trade name) to a thickness of 50 m as an adhesive, hold at a temperature of 180 for 30 minutes, and heat cure.
  • the ultraviolet-curable resin composition prepared above was applied to the pre-treated substrate using a curtain flow coater so that the film thickness after drying was 30 to 35 mm, and then heated with 80'c hot air. After drying for 20 minutes, a resin film was formed to produce a laminate. 'After cooling, put a mask for pattern exposure and Step Tablet No. 2 (Eastman Kodak Co.) on a tack-free laminate that allows close contact of the negative film.
  • a high pressure mercury lamp manufactured by Oak Manufacturing Co., Ltd. was used to irradiate light of 500 ⁇ / ⁇ > !.
  • a substrate with resist pattern formed is immersed for about 15 hours in the electroless copper plating solution maintained at 70 with the following composition, and a copper plating layer with a thickness of 30 to 35 m is extruded to produce a circuit board. did. Copper sulfate: 0.04 mol 2.2
  • Table 2 shows the evaluation test results.
  • the tackiness of the laminate prepared in the step C was observed by finger touch according to JIS-K-5400.
  • tacky items are indicated as tacky by touch, and non-sticky items are indicated as tack free.
  • step C the number of remaining steps of the stepped-blot contact portion of the sample subjected to the development treatment and the pattern width of the negative-film contact portion for the photographic resolution pattern were measured.
  • step D those with no sticking out on the resist film and those that fall off by washing with water even if a small amount of sticking out are regarded as good, and a large amount of metal on the resist film.
  • Table 2 shows that the wood came out and could not be easily removed by washing.
  • H-7 A- -4 100 B-1 0.2 Tack free H- 8 A--b 100 B-1 0.2 Tack free H-9 A--b 100 B-2 0.2 Tack free CH- 1 A--i 100 B-4 0.2 --- Tack-free CH- 2-1 100 B-1 100 10 0.4 --- Tatsuki CH- 3-1 100 B-5 0.2 Tack-free CH-4-i 100 B-1 Anti-Anti-Anti-Blended Blended Blended Blended Blended Blended 0.2 Tack-free CH-5 100 B-1 Tack-free Respond-to-respond-to-response
  • the photosensitive characteristics are excellent, and a fine resist pattern can be formed.
  • the formed resist has high surface hardness and excellent adhesion to the substrate. In addition, it has excellent electrical properties, heat cycle resistance and solder heat resistance required for permanent registry.
  • plating resist ie, plating liquid resistance, solvent resistance, plating bath contamination, and abnormal plating out-prevention are extremely excellent.
  • the resin composition containing the thiol group-containing polybutadiene derivative of the present invention can be used also as a thermosetting resist tongue, and a circuit board can be manufactured by a conventional method using the same. .
  • the thiol group-containing polybutadiene derivative and the resin composition containing the derivative according to the present invention are very stable derivatives and compositions as shown in the above Examples.
  • this boritiol compound is reacted with a resin having a butadiene chain as a main chain skeleton under specific reaction conditions, and 30 to 70% of the thiol groups in the reaction product are converted into free thiol groups. It has been stabilized.
  • the thiol group-containing polybutadiene derivative of the present invention and the resin composition containing the derivative are thermosetting and radiation-curable as shown in the above Examples, and can be used in a wide range of fields.
  • UV curable resin compositions containing a photopolymerization initiator or the like are used as resist films, especially in tackiness, in the production of circuit boards by the additive method. It is extremely suitable for forming a dist film.
  • the resist film is used for a normal resist film, for example, a protective film for a circuit, a solder resist film, and has surface hardness, adhesion to a substrate, heat cycle resistance, solvent resistance, and various properties. Satisfies electrical characteristics sufficiently.
  • the dry coating film of the composition is tack-free, it can be subjected to close contact exposure and has excellent photosensitive properties, so that a fine pattern can be formed.
  • the excellent resistance of the plating solution, the prevention of abnormal plating and the contamination of plating bath required for the plating film are extremely high. It is extremely useful as a registry for plating.

Abstract

Une composition à base de résine comprenant un nouveau dérivé de polybutadiène contenant un groupe thiol libre peut être vulcanisée par l'application de chaleur ou d'un rayonnement (notamment des rayons ultraviolets) pour produire un produit vulcanisé possédant d'excellentes propriétés chimiques, physiques et mécaniques, notamment d'excellentes propriétés de photosensibilité. Le film vulcanisé présente une excellente résistance à une solution de revêtement non électrolytique ainsi qu'une excellente capacité de prévenir tout revêtement anormal pendant une opération de revêtement non électrolytique, ce qui le rend tout indiqué pour former des films de revêtement de réserve dans le processus de production de cartes de circuits selon un procédé d'addition. La composition décrite permet d'obtenir des cartes de circuits de haute densité grâce à ses excellentes propriétés de photosensibilité, notamment à son excellent pouvoir résolvant.
PCT/JP1985/000295 1985-05-29 1985-05-29 Derives de polybutadiene contenant un groupe thiol, composition a base de resine les contenant, procede de preparation de ces derives et de cette composition a base de resine, et procede de production de cartes de circuits WO1986007071A1 (fr)

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PCT/JP1985/000295 WO1986007071A1 (fr) 1985-05-29 1985-05-29 Derives de polybutadiene contenant un groupe thiol, composition a base de resine les contenant, procede de preparation de ces derives et de cette composition a base de resine, et procede de production de cartes de circuits

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Application Number Priority Date Filing Date Title
PCT/JP1985/000295 WO1986007071A1 (fr) 1985-05-29 1985-05-29 Derives de polybutadiene contenant un groupe thiol, composition a base de resine les contenant, procede de preparation de ces derives et de cette composition a base de resine, et procede de production de cartes de circuits

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008231409A (ja) * 2007-02-19 2008-10-02 Mitsubishi Rayon Co Ltd 硬化性組成物及びその硬化物
JP2011202070A (ja) * 2010-03-26 2011-10-13 Dic Corp 硬化性樹脂組成物及びその硬化物

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5558226A (en) * 1978-10-03 1980-04-30 Lankro Chem Ltd Photoopolymerizing composition*its manufacture and its use

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5558226A (en) * 1978-10-03 1980-04-30 Lankro Chem Ltd Photoopolymerizing composition*its manufacture and its use

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008231409A (ja) * 2007-02-19 2008-10-02 Mitsubishi Rayon Co Ltd 硬化性組成物及びその硬化物
JP2011202070A (ja) * 2010-03-26 2011-10-13 Dic Corp 硬化性樹脂組成物及びその硬化物

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