WO1986007071A1

WO1986007071A1 - Thiol group-containing polybutadiene derivatives, resin composition containing same, process for preparing said derivatives and said resin composition, and process for producing circuit board

Info

Publication number: WO1986007071A1
Application number: PCT/JP1985/000295
Authority: WO
Inventors: Masayuki Kataoka; Yukio Yamase; Masami Yamazaki
Original assignee: Nippon Soda Co., Ltd.
Priority date: 1985-05-29
Filing date: 1985-05-29
Publication date: 1986-12-04

Abstract

A resin composition comprising a free thiol group-containing novel polybutadiene derivative can be cured by applying heat or radiation (particularly UV rays) to produce a cured product having excellent chemical, physical, and mechanical properties, particularly excellent photo-sensitive properties. The cured film has an excellent resistance against an electroless plating solution and has an excellent ability of preventing abnormal plating upon electroless plating, thus being suited for forming plated resist film in the process of producing circuit boards according to additive process. The composition provides high-density circuit boards because of its excellent photo-sensitive properties, particularly excellent resolving power.

Description

Specification

1 Title of invention

Thiol group-containing polybutadiene derivative, having the derivative

A resin composition, the derivative, a method for producing the resin composition,

And a method of manufacturing a circuit board

2 Detailed description of the invention

〔Technical field〕

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.

More specifically, 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.

Therefore, 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.

(Background technology)

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.

Many patents have been published or published on the circuit board manufacturing method by the additive method. "Practical surface technology · P7-8 (1980)", "Electronic technology, Vol.23, No.14, P108-111" "Electronic technology, Vol.24, No.4, P92-95" You will be able to get an overview of the information through such means.

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.

Therefore, in the additive method, a resist for forming a circuit pattern, that is, a plating resist is required to have a performance that can withstand the plating condition. In addition, since 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.

Therefore, 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. As 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. However-In recent years, 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.

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. -'

(A) Since the resist resin of the dry film is semi-solidified in advance, the adhesiveness to the substrate is inferior to that of the liquid resist resin.

Therefore, the formed resist pattern is likely to have a defect.

(B) Due to the tackiness of the resist surface, it is difficult to adhere the negative mask directly. However, the resolution is inferior to the method in which a negative mask is directly adhered to the resist surface and exposed.

It is difficult to fabricate fine patterns.

(C) The problem of tackiness and resolution can be solved by off-contact and parallel exposure methods. However, there is no large off-contact, parallel exposure type large-area light source that can be applied to large substrates (600 mm X 600 mm). In addition, this type of exposure unit is generally expensive, so that it is difficult to employ it industrially. Generally, gay citrate-based and cyclized rubber-based resists are known as contact exposure type resists, but these are all etching resists, and the thickness of the resist is 10 m or less. Also, it does not have coating properties that can withstand electroless copper plating.

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.

In the composition, 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. However, since 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. . In addition, the document discloses that 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.

On the other hand, the present inventors have previously disclosed in Japanese Patent Application No. 57-193521 (see Japanese Patent Application Laid-Open No. 59-86045) a urethane (meta metal) having a 1,2-polybutadiene as a main chain. We have proposed a photocurable resin composition for permanent resist, which is mainly composed of acrylic resin.

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).

However, 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.

In order to improve this point, as a result of mixing a thiol-based compound with the perethane (meth) acrylate resin, the electroless plating in the production of a circuit board by the additive method has been achieved. A photocurable resin composition suitable as a photo resist for use was obtained. However, 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.

[Disclosure of the Invention] 'The present inventors have conducted intensive studies to achieve the above object. Polybutadiene urethane (meta) acrylate resin having an acryloyl group of: 1 mole or less of a polythiol compound was reacted with 1 mole or less of a thiol-modified polybutadiene derivative. A novel thiol-containing polybutadiene derivative in which 30 to 70% of the thiol groups possessed by the polythiol compound is present as a free thiol group is extremely stable, and a resin composition having the derivative is As a photo resist for electroless plating by the additive method, they have found that they have extremely excellent properties, and have completed the present invention. In the present specification, the first invention has a general formula:

(H „

(here,

R is a divalent organic residue

Is one H or one CH ₃ ,

U is a urethane bond-N-C-0-,

H I 0 II,

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. ゥ butadiene diol reaction residue,

Y is a urethane-reactive residue of a polyol compound having 3 to 4 hydroxyl groups per molecule, and

Z represents a urethane-reactive residue of the diisocyanate compound, and n represents an integer of 2 to 3. ), The urethane-based unsaturated resin [A];

General formula: IT "" SH) _m (2)

(Where R "represents an organic residue with a molecular weight of 80-1000,

m represents an integer of 2 to 4. )

A polythiol compound [B] represented by the formula:

It is a thiol-based polybutadiidine derivative obtained by reacting 30 to 70% of the thiol groups as free thiol groups so as to remain after the reaction. The second aspect is a resin composition having the thiol-based polybutadiene derivative.

More specifically, 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:

(Where Β, Β ', U, Y, Z and η represent the same meaning as above,

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. ) The urethane-based unsaturated resin [Α '] represented by

The urethane-based unsaturated resin [Α ');

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 [Α '] represented by the general formula (lb). 1 mole of a mixed urethane-based unsaturated resin;

0.1 to 1 mol of 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. A method for producing the thiol-based polybutadiene derivative and a resin composition having the derivative, wherein the reaction is carried out with stirring and holding.

According to a fourth aspect of the present invention, 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. A step of forming a circuit pattern, a step of forming a circuit pattern by an electroless plating method,

And a method for manufacturing a circuit board.

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.

In this derivative, 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.

Furthermore, 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.

If the ratio of one-to-two bonds is low, the objective cannot be achieved. In particular, when the 1 * 2—bond is 80% or more, a resist having excellent curability and hardness can be obtained as a final product. In the derivative, 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. In the derivative, 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.

In addition, through these urethane bonds, two or three (meth) acryloyl groups are present at both ends of the butadiene skeleton of the main skeleton. Is an important factor for having flexibility and exhibiting excellent impact resistance.

In the derivative, 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.

In the derivative, when 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.

When the free thiol group content is less than 30%, the curability and the photosensitive properties as a photo resist are extremely reduced. On the other hand, when the free thiol group exceeds 70%, the stability is lowered and the gel is easily formed.

If 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. On the other hand, when 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.

Further, when a compound having the number of thiol groups represented by m in the general formula (2) of 1 is used, 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).

As the boron compound [B], 1 · 2-ethanedithiol, 1 • 2—pronodithiol, 1,3—pronodithiol, hexamethylenedithiol, p ^ nzen Examples thereof include dithiol and xylylenedithiol. In addition, esterification reaction of mercaptocarboxylic acids such as thioglycolic acid, -mercaptopropionic acid, and β-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. Glycol, 1.3—butanediol, 1.6 ^ xandiol, neopentyl glycol, bisphenol Α, hydrogenated bisphenol ,, bisphenol A-ethylene Benzoic acid adduct, bisphenol A—propylenoxy adduct, thiodiethanol, trimethylol propylone, trimethylol pentane, glycerin, tris Ethanolamine, Pentaerythritol, Sorbitol, Neudroquinone, Pyrogallonole, Xylene glycol, 4,4'-Dihydroxyphenylmethane, Examples include lishydroxyshethyl citrate, bishydric chelshylhydantoin, and polyethylene glycol with an average molecular weight of 1000 or less, glycol and polypropylene glycol. can do.

Further, 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. Dalico dimercaptoporionic esters obtained by an esterification reaction of mercaptopropionic acid with glycols, from which an excellent resin is obtained.

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.

In the second invention, 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. Instead of the chain, the urethane reaction residue of at least one diol compound selected from the group consisting of polyether diols, polyester diols and polyacryl diols having a number average molecular weight of 200 to 5000 A urethane-based unsaturated resin [Α ′] represented by the general formula (lb) having a main chain skeleton as a group, or a polythiol-modified derivative of the urethane-based unsaturated resin. When 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. In addition, in the case of ultraviolet curing, the thermosetting properties after exposure and development are reduced, and the desired coating film properties cannot be obtained.

Typical specific examples of the diol compound 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.

Accordingly, 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. When the composition is used for forming a resist of a circuit board, which is the final object of the present invention, it is preferable to use 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. , 4——Methoxy benzophenone, 4 · 4 ′ —— Dimethyl benzophenone, 4——Brombenzofenone, 2.2 · 2 ′, 4.4 · ——— Tetrachloronobenzophenone 2-, 1-chloro-4'-methylbenzophenone, 3-—methylbenzophenone, 4-—t-butyclevenzovanone, benzinole, benzinoleic acid, diacetinole, methylenblue, a Set phenonone, 2 · 2 —— Diethoxy phenonone, 9 · 10 — — phenanthrenquinone, 2 — — methylan Traquinonone, 2-—ethylantraquinone, 2-—t-butylantraquinone, diphenyldisulfite, dithiocananomate, or—chloronomethylnaphthalene, anan These include thracene, iron chloride, and 1,4-naphthoquinone. In particular, 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.

Further, 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, Ν, Ν'-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. In order to suppress crosslinking, a polymerization inhibitor (stabilizer) is preferably added.

Stabilizers such as di-t-butyl-p-cresol, nodroquinone monomethyl ether, pyrogallol, quinone, noidroquinone, t-butynole, and nodroquinone monobe For example, benzoquinone, methinolenoid hydroquinone, amylquinone, phenol, phenolic quinone monobutyl butyl ether, phenolic thiazine, and nitrobenzene are used.

If desired, various additives can be uniformly dissolved in the composition or can be added in the form of a heterogeneous compound. Examples of these 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)

The urethane unsaturated resin [A] represented by the general formula (la) alone or the urethane unsaturated resin [A] and the urethane unsaturated resin [A] represented by the general formula (lb) While blowing an oxygen-containing gas into the organic solvent solution of the mixture with the unsaturated resin [Α '], a predetermined amount of the boritiol compound [Β] 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.

In the reaction, 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. When the reaction temperature exceeds 100, a derivative having better storage stability is obtained, but the reaction itself becomes unstable and gelation easily occurs. When 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.

In the present invention, 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.

Ag (NH ₃ ) ₂ ⁺ + RSH RSAg + NH ₄ ⁺ + NH ₃

In the present invention, the urethane-based unsaturated resin [A] represented by the general formula (la) as a raw material is represented by the following general formula:

H0-^-X-^-0H (3a)

(Where X represents the same meaning as described above.) A polybutadienediol [C] represented by the following general formula:

Y- -UZ-NC0) „ ₊ , (4)

(Where Υ, Ζ, ΙΙ, and η have the same meanings as described above.) A urethane polymer [D] represented by the following general formula:

(Where 8 and R ′ have the same meanings as described above.) In general, the compound is synthesized from the (meth) acrylate compound [Ε] according to the reaction formula shown below. Is done. (Ηθ-ί-Χ- -ΟΗ + 2Y- -UZ-NC0) „ _{+ 1} -diol (C) prepolymer (D)

Polyisocyanate compound [F]

Polyisocyanate compound [F] (meta) acrylates [E] (H ₂ C = CC-0-RUZU-- _ff -YUZUX _π

ι, ιι

δ '0 [II]

UZUY-^-UZU- -0-CC = CH ₂ ) _η

0 II R I '

Urethane unsaturated resin [Α]

In the above reaction, instead of polybutadienediol [C], the following general formula:

H0--X '-)-0H (3b)

(Where X ′ has the same meaning as described above.) By using the polyether diol [C ′] represented by the formula (1), a urethane-based unsaturated resin [Α ′] can be obtained. Can be

In the reaction, 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 [Α ']. An unsaturated resin is obtained.

The number of hydroxyl groups in polybutadiene diol [C] and polyether diol [C '] should be, as a rule, 2 原則 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.

In order to introduce a large number of polyurethane resins into the urethane-based unsaturated resin, tri- or tetra-valent polyol compounds are used. Sometimes it is easy to gel, and its curing properties are not necessarily improved.

As the trivalent or tetravalent polyol compound, those having a molecular weight of 2000 or less are usually used. For example, glycerin, 1 · 2 * 6.xantholyol, 1 ♦ Γ1 11 trimethylolpropane, 1 · 1 11 trimethylolonetan, trietanoylamine , Triisopronodiol, phenolamine, pentaerythritol, and the like, and these compounds can be used as a mixture of two or more kinds as necessary.

On the other hand, as 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, 4 · 4 '-— Methylene hydride (cyclohexyl citrate), methyl cyclohexane 2 * 4 — Diisocyanate, methyl hex 2 6—Diisocyanate, 1.3— (Isocyanate methyl) Cyclohexane, Isophorone diisocyanate, Trimethyl hexylene diisocyanate, Dimer Examples include acid diisocyanate, phenolic diisocyanate, 2-hydroxyl-1.4-phenyldiisocyanate, and 1.5-naphthalene diisocyanate. They can be used alone or as a mixture of two or more.

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. When the reaction ratio is out of the above range, gelation is very likely. 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. When 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 [Ε] 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. In the production of the urethane-based unsaturated resin represented by the above reaction formula, the reaction solvent is a hydrocarbon, ester, ketone, ether, halogen, which does not have active hydrogen that reacts with the isocyanate group. Use hydrogenated hydrocarbons and mixtures thereof. Specifically, 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. One or a mixture of two or more of halogenated hydrocarbons and aromatic halogenated hydrocarbons such as chlorobenzene and 0-dichlorobenzene are used.

These reactions are performed in the presence of a known urethanization catalyst. As urethanization catalysts, tertiary amines such as triethylamine, triethylene diamide, and dimethyl morpholine, and 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. In particular, the composition is suitably used for forming a metal resist in the production of a circuit board by an additive method.

According to a fourth aspect of the present invention, there is provided 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.

In the present invention, 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. In another embodiment, 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.

Then, a negative mask on which a circuit pattern is printed is brought into close contact with the resin film formed on the substrate, and irradiated with ultraviolet light. 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.

After the exposure is completed, 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.

According to the above method, 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.

Next, 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. You. In this case, 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. '

[Best mode for carrying out the invention]

The present invention will be described in more detail by way of examples.

However, the following examples show one embodiment of the invention, and the scope of the present invention is not limited to the following examples.

In the following examples, parts and% are based on weight unless otherwise specified. .

Example 1 (Synthesis of urethane unsaturated resin)

[Sample A-l]

In a reaction vessel equipped with a stirrer, gas blow-in pipe, dropping funnel, thermometer and reflux condenser, 1 1 1 1-trimethylolpropane; 60 parts, 2-4 4-triethylene succinate: 80 % And 2-6-trirange isocyanate: 20% by weight mixed trirange isocyanate; 240 parts and n-butyl acetate; 120 parts are charged, and after nitrogen replacement, gradually stirred. Then, the mixture was maintained at a temperature of 80 for 2 hours to synthesize a compound corresponding to the urethane prepolymer [D] represented by the general formula (4).

Then, toluene; 370 parts, diethyl acetate; 90 parts, n-butyl acetate; 90 parts and ethylene glycol monoethyl ether acetate; 470 parts of a mixed solvent consisting of: a number-average molecular weight: 2,000, a hydroxyl value: 50 (K0H mg / g, the same applies hereinafter), a polybutadiene diol having 91.7% of butadiene units of a polymer chain in a 1 / 2-bond; Was added dropwise to the urethane blebolimer reaction solution over a period of about 2 hours.After the completion of the dropwise addition, the temperature was further increased to 80'c while passing a small amount of nitrogen gas into the reaction vessel. The reaction was maintained for 2 hours, and the polyisocynate compound [F] was synthesized.

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-2)

In the synthesis of Sample A-1, the synthesis of Sample A-1 was repeated except that 130 parts of 2-Hydroxyshetyl metal acrylate was used instead of 2-Hydroxyshetyl acrylate. The reaction was carried out under the same conditions as described above to obtain a urethane-based unsaturated resin [A-2] with a residual NC0 of 0.02%.

(Sample A-3)

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%.

(Sample 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.

Then, 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 A solution prepared by previously dissolving 73.6 parts of propylene glycol, a molecular weight of 700, was dropped into the reaction solution of the urethane prepolymer over about 2 hours. After the completion of the dropping, nitrogen gas was introduced into the reaction vessel. While passing through a small amount, the reaction was maintained at a temperature of 80 for another 4 hours to surround the reaction, thereby synthesizing a boronic acid compound.

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 [樹脂 -4] with a residual NC0 of 0.02%.

(Sample A-5)

In the same reaction vessel used for the synthesis of sample A-1, glycerin; 18.4 parts, mixed tri-range succinate of the same specification used for the synthesis of sample A-1; 104.5 parts and η-butyl acetate 52.7 parts were charged, and after purging with nitrogen, the mixture was gradually heated with stirring and kept at a temperature of 60'c for 3 hours to synthesize a urethane prepolymer.

Then, η-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%.

[Sample 'A-6]

The same reaction vessel used for the synthesis of Sample A-1 was charged with 348 parts of the same mixed tri-range sodium used for the synthesis of Sample A-1; 348 parts and n-butyl acetate; and 348 parts of acetic acid. n-Butyl; 68 parts of pentaerythritol; a solution prepared by dissolving 68 parts in advance is added. After purging with nitrogen, the mixture is gradually heated with stirring, kept at 80 at room temperature for 2 hours, Was synthesized.

410.5 parts of n-butyl acetate; number-average molecular weight: 1,500; hydroxyl value: 66.6; polybutadiene diol, in which 91.7% of butadiene units in the polymer chain are composed of 1 / 2-bonds; The dissolved solution was added dropwise to the urethane prepolymer reaction solution over about 2 hours.After the addition was completed, the temperature was kept at 80 for 4 hours while passing a small amount of nitrogen gas into the reaction vessel. By continuing the reaction, a polyisocyanate compound was synthesized. The resulting polyisocynate compound is free isocynate. Was 3.9%, and the viscosity was S.

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%.

(Comparative sample CA-1)

In the synthesis of Sample A-4, the same conditions as in the synthesis of Sample A-4 were used, except that aryl alcohol; 58.1 parts was used instead of 2-hydroxylacrylate. To obtain a urethane-based unsaturated resin [CA-1] having an aryl group at the terminal with a residual NC0 of 0.02%.

[Comparative sample CA-2]

In the synthesis of Sample A-4, the reaction was carried out under the same conditions as in the synthesis of Sample A-4, except that the reaction amount of 2) hydroxyshetyl acrylate was changed to 94 parts. : 0.5% urethane-based unsaturated resin [CA-2] having free NC0 groups was obtained.

(Comparative sample CA-3)

In the synthesis of Sample A-4, except that the amounts of n-butyl acetate, polybutadiene alcohol and polypropylene propylene glycol used were 213 parts, 106.6 parts and 106.6 parts, respectively, The reaction was carried out under the same conditions to obtain a pale yellow, transparent solution-like polysocyanate compound containing 3.9% of free isocyanate and having a viscosity of C.

Then, while switching the gas introduced into the reaction vessel to dry air and passing a small amount of gas, 110 parts of 2-hydroxyhexyl acrylate from the dropping funnel was added to the reaction solution of the polyisocyanate over 2 hours. After completion of the dropwise addition, the reaction was maintained at a temperature of 80 for an additional 3.5 hours to complete the reaction, and the remaining NC0: 0.01% of a mixed urethane-based unsaturated resin with a prevalence of 50 系 (less than 60%) of a urethane-based unsaturated resin having a butadiene resin corresponding to the synthesized A-1 as a main skeleton. Resin [CA-3] was obtained.

(Comparative sample CA-4)

The 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.

Then, 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. A solution in which 401.3 parts of an impregnated (hydrogenation ratio: 95%) polybutadiene diol was sufficiently dissolved in advance was added dropwise over 2 hours to the reaction solution of the synthesized urethane prebolimer. After the completion of the dropwise addition, the temperature was kept at 80 at the temperature of 80 for 4 hours while introducing a small amount of nitrogen gas into the reaction vessel to obtain a polyisocyanate compound.

The obtained polysocyanate compound was a light yellow transparent liquid having a free isocyanate content of 2.9% and a viscosity of Τ.

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.

[Comparative sample CA-5]

Acetic acid _η -butyl; 347 parts, number average molecular weight: 2,800, hydroxyl value: 48.4, butadiene unit of polymer polymer 1-2-bond: 0.2 mol, 1-4 single bond: 0.8 mol of polybutadiene diol (Poly BD-45GT, manufactured by Idemitsu Petrochemical Co., Ltd.); a solution in which 347 parts were well dissolved in advance was synthesized under the same conditions as the comparative sample CA-4. The reaction solution was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was kept at 80 at the same temperature for 4 hours while introducing a small amount of nitrogen gas into the reaction vessel to obtain a polyisocyanate compound.

The obtained polysocyanate compound was a pale yellow transparent liquid having a free isosilicate: 3.5% and a viscosity: V.

The nitrogen gas introduced into the reaction vessel was switched to dry air, and from the dropping funnel, 125 parts of 2-hydroxyshetyl acrylate; 125 parts were added dropwise over 2 hours. After the addition was completed, the temperature was raised to 80. The reaction was continued for 3.5 hours, and the remaining N.C0: 0.02% of the urethane-based unsaturated resin [CA5] containing less than 50% of the 1.2-bond of the butadiene unit constituting the main skeleton was used. Obtained. · '[Comparative sample CA-6]

In 150 parts of n-butyl acetate, a solution of 150 parts of poly (propylene glycol) having a number average molecular weight of 700 and a hydroxyl value of 160 was dissolved well in advance under the same conditions as Comparative Sample CA-4. It was added dropwise over 2 hours to the reaction solution of the synthesized polymer. After the completion of the dropwise addition, the temperature was kept at 80 at the temperature of 80 for 4 hours while introducing a small amount of nitrogen gas into the reaction vessel to obtain a polyisocyanate compound.

The obtained polyisocyanate compound was a pale yellow transparent liquid having a free isocyanate content of 4.5% and a viscosity of D.

The nitrogen gas 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 for another 3.5 hours at the temperature, and the urethane unsaturated corresponding to [Α '] represented by the general formula (lb) Resin [CA-6] was obtained.

(Comparative sample CA-7)

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.

NC0: 12.5% of hydroxy-shetyl acrylate product was obtained.

Then, 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%.

(Comparative sample CA-8)

Η-butyl acetate; 245 parts, 700 mole weight polyether triol based on propylene oxide and glycerin having a hydroxyl value of 242, (PPG-MN-700 · Mitsui Nisso Sourethane 100 parts of a well-dissolved solution was charged into a reaction vessel, gradually heated to 50 under a nitrogen atmosphere, and then mixed with the above-mentioned comparative sample CA-7. 145 parts were dropped over 1 hour. The reaction temperature was raised to 70'c, and the reaction was aged by keeping the mixture under stirring for further 4 hours to obtain a urethane unsaturated resin [CA-8] having a residual NC0 of 0.02%.

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 [Α-1 to Α-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. Was.

For comparison, the 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.

(Stability test)

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.

(Hereinafter the margin) Table i

Urethane-based unsatisfactory Polythio-reactor can Reaction conditions 鰂 Cho stability test No. Species quantity Species quantity Quantitative ha. Bt. Time?み A temperature temperature time feeling

(Part) (part) (&) (• C) (Hr) Gas i%) Cc) (Saying)

G-1 A--1 100 B--1 3 10 50 5 63 50 10 No abnormality

G-2 Α-2 100 B-2 5 10 70 4 47 50 10 No abnormality

G-3 A-3 100 B- -1 5 10 80 4 57 50 10 No abnormality

G-4 A--4 100 B--1 4 2000 70 6 52 50 10 No abnormality G-5 A-4 100 B--2 4 2000 80 5 59 50 10 No abnormality

G-6 A-4 100 B-3 3 200 80 6 ^ 48 50 10 No abnormality Example

G-7 A--4 100 B-1 5 200 60 6 62 50 10 No abnormality

G-8 A-5 100 B-1 4 200 70 6 45 50 10 No abnormality

G-9 A-6 100 B-2 4 200 70 6 ^ 43 50 10 No abnormality

CG-1 A--1 100 B--1 3

¹ ^ SSi 1 Keno Wt:

CG-2 A--2 100 B--2 5

¹ ^ 1 Geno W danger ratio CG-3 A-3 100 B- -1 5 .m. 10

CG-4 A-4 100 B-1 4 50 3

CG-5 A-4 100 B-3 3 130 Medium gel Example CG-6 CA-2 100 B-3 3 0.2 Kaburagi 1 Gelation

CG-7 A-4 100 B-1 6 Sense 0.5

CG-8 A-4 100 B--2 5 50 Mixed gel

As shown in Table 1, 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.

In contrast, the system [CG-5] with a reaction temperature of 130'C and the system [CG-8] with a heating reaction in a nitrogen atmosphere gel during the reaction.

When the reaction temperature or the reaction time is insufficient, the reaction between the urethane unsaturated resin [A] and the polythiol compound [B] does not proceed, and the free thiol groups in the resin composition may be excessive. Therefore, only an extremely unstable composition can be obtained.

Example 3 [Manufacture of circuit board-formation of plating resist]

(A) Preparation of UV-curable resin composition

100 parts of each of the resin compositions [Gl to G-9] synthesized in Example 2 were mixed with 5 parts of benzyl dimethyl ketal as a photopolymerization initiator and 0.2 parts of a phthalocyanine pigment. Then, an ultraviolet curable resin composition [H-1 to Η-9] was prepared.

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.

Further, the same additives as G-1 to G-9 were blended with the urethane-based unsaturated resin A-4 synthesized in Example 1, and an ultraviolet curable resin for comparison was used. A composition [CH--14] was prepared.

(B) Pretreatment of substrate

On a glass epoxy substrate surface, apply a 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. Was.

Then, it was immersed in a mixed solution of chromic acid 300 g / and sulfuric acid 200 g / at 60 for 15 minutes to perform a surface roughening treatment, and then a Pd catalyst treatment for electroless plating was performed.

(C) Formation of the resist

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 500π / α> !.

After leaving at room temperature for 20 minutes, using a spray developing machine, develop for 2 minutes with 1.1 • 1-trichloroethane solvent, then wash with methanol, then heat to 160 The substrate was held for 30 minutes and cured by heating to form a resist pattern on the substrate.

(D) Formation of electroless net circuit

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

E.D.T.A .: 0.10 mol Cyanated Caliform 20 mg Formalin: 0.10 mol Surfactant 1.0 mg (E) Evaluation test

In each of the above steps, the following evaluation tests were performed.

Table 2 shows the evaluation test results.

(a) Tackiness of dried coating film

The tackiness of the laminate prepared in the step C was observed by finger touch according to JIS-K-5400.

In Table 2, tacky items are indicated as tacky by touch, and non-sticky items are indicated as tack free.

(b) Photosensitivity characteristics

In the 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.

(c) Surface hardness and adhesion of resist film

Based on JIS-K-5400, the measurement of pencil hardness and the Goban separation test were performed.

(d) Heat cycle property of resist film

After a heat cycle test of 125'c at -65, it was visually observed after 100 cycles. (Based on JIS-C-6491)

Those which did not show any cracks by visual observation are shown in Table 2 as 0K.

(e) Solder heat resistance of resist film

After immersion in a solder bath at 260 for 30 seconds, they were visually observed. (Compliant with JIS-C-648 1) Those that did not show cracks, blisters, etc. by visual observation were shown in Table 2 as 0K.

(f) Normal state and dielectric constant of electrical insulation resistance of resist film

In accordance with JIS-C-6481, the electrical insulation resistance (Ω) under normal conditions and the dielectric constant (s) at 1MH2 were measured.

(g) Resistant property of resist film

After immersion in the chemical copper plating solution (pH = 12.5) used in the step D at a temperature of 70′c for 20 hours, a change in appearance was observed.

Those with no abnormal appearance are indicated in Table 2 with a triangle.

(h) Solvent resistance of resist film

After immersion in boiling boiling water for 5 minutes, changes in appearance were observed and an adhesion test (based on JIS-D-0202) was performed. .

Those with no abnormal appearance are indicated in Table 2 with a triangle.

(i) Abnormal sticking out

In the above-mentioned 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.

(j) Meat liquid contamination

After repeating the electroless copper plating operation in the step D using the substrate on which the same resist is formed ten times, observe the appearance of the plating liquid and the presence or absence of the protruding material in the plating liquid. did. Trial number Table 2

No. Urethane-based, Politics

Species mass Species mass-mixed (meta) ac

(Part) (Part) Rilmonomer I Zhong ^ Γ 开 Measure tackiness

—H- 1 A-1 100 B-1 3 5 0.2 Tack-free H- 2 Α- -I 100 B-2 5 0.2 Tack-free H- 3 ft- -3 100 B-1 5 0.2 Tack-free — H- 4 ft- -4 100 B-1 0.2 Tack free H- 5 A- -4 100 B--2 0.2 Tack free H- 6 A- -4 100 B-3 0.2 Tack free Example

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 Blended 0.2 Tack-free CH-5 100 B-1 Tack-free Respond-to-respond-to-response

Ratio

CH- 6 CA- -3 100 B--1 0.2 Tack-free CH- 7 CA- -4 100 B-3 0.2 Tack-free CH- 8 CA- -5 100 B-2 0.2 Tuck-free CH- 9 CA- -6 100 B--2 0.2 Tack-free example

CH-10 CA- -6 100 B-3 100 0.4 Tatsu eleven CH-11 CA- -7 100 B-1 0.2 --- Tatsu; j CH-12 CA- -8 100 B-5 0.2 -13 CA- -8 100 B-5 100 10 0.4 "

Table 2 (continued) Sample Photosensitivity Characteristics Film physical properties Chemical resistance Abnormality No. No. Residual film resolution Lead and brush Heatsa Solder 腿 Thigh magnetic susceptibility Metriclicene Metzki Number of bath steps (Mm) Hardness Iku 賺 re (cross cut) 賺 10 ' ⁵ Ω £

H- 1 9 40 50 6H 0K 0K 100/100 21.0 2.2 OK 〇 100/100

H- 2 7 40 50 6H 0K OK 100/100 23.0 2.3 OK 〇 100/100

H- 3 9 40 50 5H 0K OK 100/100 15.0 2.3 0K 〇 100/100 mm

H-4 9 40 50 5H 0K OK 100/100 60.0 2.6 OK 〇 100/100 m

App.H- 5 9 40 50 5H 0K OK 100/100 50.0 2.7 OK 〇 100/100

H- 6 9 40 50 6H 0K 0K 100/100 70.0 2.6 OK 〇 100/100

Example m

H- 7 9 40 50 5H 0K 0K 100/100 17.0 2.6 0K 〇 100/100

H- 8 8 40 50 5H 0K 0K 100/100 18.0 2.2 OK 〇 100/100 m

H- 9 8 40 50 6H 0K OK 100/100 20.0 2.3 OK 〇 100/100 m i-

CH- 1 2 X 2H X X 50/100 5.5 3.2 X X 0/100 Poor turbidity

CH-2 6H 0K 0K 50/100 0.6 4.0 X 〇 0/100 defective Cloudy

CH-3 5 120 140 7H X X 0/100 2.1 2.6 X 〇 0/100

CH- 4 2 X 4H X 0K 0/100 2.2 2.9 X 〇 0/100 defective Cloudy

CH-5 2 X 5H OK OK 80/100 2.3 2.3 OK 〇 50/100 Defect ratio

CH-6 6 100 120 4H X 0K 50/100 0.4 3.5 X 〇 0/100 defective

CH-7 4 X B X X 50/100 3.3 2.8 X X 0/100 Poor turbidity comparison

CH- 8 4 X HB X X 0/100 4.5 3.2 X X 0/100 Poor turbidity

CH-9 5 120 140 4H X οκ 100/100 0.32 3.5 X X 0/100 Poor port Example

CH-10 7H X OK 70/100 0.65 3.9 X O 0/100 defective Cloudy

CH-11 5H X X 30/100 2.2 2.4 X X 0/100 Poor turbidity

CH-12 6H X OK 70/100 0.72 3.8 X 〇 50/100 defective Cloudy

CH-13 7H X 0K 100/100 0.32 3.9 X 〇 80/100 defective Cloudy

As shown in Table 2, in the system using the resin composition (Η-1 to Η-9) containing the thiol group-containing polybutadiazine derivative of the present invention, the dried coating film was tack-free, As a result, contact exposure is possible.

Also, 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.

In particular, various properties as a plating resist, ie, plating liquid resistance, solvent resistance, plating bath contamination, and abnormal plating out-prevention are extremely excellent.

On the other hand, in the system (CH-1 ′ to CH-13) using a known composition as a conventional resist, all of the required characteristics are satisfied even if some of these required characteristics are added. There is no.

In addition, the system [CH--14], which does not contain a thiol compound in the urethane-based unsaturated resin synthesized as Sample A-4, satisfies many of the characteristics required for plating resists. The characteristics (resolution) are not sufficient, and there is also a problem in preventing abnormal plating from popping out.

Example 4 [Thiol-based polybutadiene derivative

Thermosetting of the resin composition containing)

A resin composition containing a thiol group-containing polybutadiene derivative synthesized as sample G-4 in Example 2; 100 parts of the resin composition was distilled under reduced pressure to remove about 1/2 of the solvent, and then a trimethylolpropane reagent was prepared. Dissolve by adding 25 parts of acrylate; further, add 4 parts of silicon oxide; 4 parts of zirconium silicate; 1.5 parts of silicon oil; and knead well using a roll mill. To produce ink. The prepared ink was screen-printed on a substrate that had been pre-processed in the same manner as in Example 3, and was heat-cured at a temperature of 160 for 40 minutes. The resulting coating had excellent gloss.

With respect to the resist film formed on the substrate, various evaluation tests were performed under the same conditions as in Example 3 and had a surface hardness equal to or lower than the surface hardness.

Each test result was equivalent to H-4.

That is, 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. .

[Industrial applicability]

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.

In particular, as shown in the comparative examples, in a resin composition having butadiene diene as a main chain skeleton, as disclosed in the prior art, it is extremely unstable and practical to simply mix a boritiol compound. It is difficult to provide for

In the present invention, 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.

In addition, since 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.

In addition, 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.

In the production of a circuit board for forming a plating resist film using the above-described composition, it is possible to form a very fine resist pattern as described above, so that a high-density circuit board can be produced. It is possible.

Claims

The scope of the claims

1 General formula:

(This V

R is a divalent organic residue,

R 'is one H or one CH ₃ ,

U is a urethane bond-N-C-0—

H 0,

X is a pentane reaction of a polybutadiene diol having a hydroxyl group at both ends with a number average molecular weight of 500 to 5000, in which at least 50% of the butadiene units in the polymer are composed of 1 · 2 bonds. Residue,

Υ is a urethane-reactive residue of a boryl compound having 3 to 4 hydroxyl groups per molecule, and

Ζ represents a urethane-reactive residue of a diisocyanate compound,

η represents an integer of 2 to 3. ), A urethane-based unsaturated resin [];

General formula: B "~" SH) _m (2)

(here,

R "represents an organic residue having a molecular weight of 80 to 1000,

m represents an integer of 2 to 4. )

A polythiol compound [B] represented by the formula:

A thiol-containing polybutadiene derivative obtained by reacting 30-70% of the thiol groups as free thiol groups so that they remain after the reaction 2 At least 60% of the resin content has the general formula:

(here,

R is a divalent organic residue, '

r is one H or one CH ₃ ,

ϋ is a urethane bond-N-C-0-

Η 0,

X is a perylene reaction of polybutadienediol having a hydroxyl group at both terminals with a number average molecular weight of 500 to 5000, which is composed of 1 * 2-bonds in which 50% or more of the butadiene units in the polymer are present) ¾: residue, '

Υ is a urethane reaction residue of a polyol compound having 3 to 4 hydroxyl groups per molecule, and

Ζ represents the ゥ -reactive residue of the diisocyanate compound,

η represents an integer of 2 to 3. .) Urethane-based unsaturated resin [Α];

General formula: R "~ i-SH) _m (2)

(here,

R "represents an organic residue having a molecular weight of 80 to 1000,

m represents an integer of 2 to 4. )

A polythiol compound [B] represented by the formula:

A thiol-based polybutadiene derivative obtained by reacting 30 to 70% of the thiol groups as free thiol groups so as to remain after the reaction,

The remaining resin is represented by the general formula: (H ₂ C = CC-0-RUZU-) nr-YUZUX ^, n

I II

R 'o

^L UZUYiUZUR-0-CC = CH ₂ ) „(lb)

! R '

(Where R, R ', U, Y, Z and n represent the same meaning as above,

Γ represents a urethane-reactive residue of one diol compound selected from the group consisting of polyether diols having a number average molecular weight of 200 to 5,000, polyester esters and polyacryl diols. ), A urethane-based unsaturated resin [Α '], or

The urethane-based unsaturated resin [Α '];

A polythiol compound represented by the general formula (lb); 0.1 to 1 mol of a thiol group obtained by reacting 30 to 70% of thiol groups as free thiol groups so as to remain after the reaction. Resin composition having poly-butadiene derivative

3 General formula:

(here,

R is a divalent organic residue,

R ′ is one or _three CH ₃ ,

U is a urethane bond-N-C-0—

I II

H 0,

X is a polybutadiene unit having a number-average molecular weight of 500 to 5,000 and having hydroxyl groups at both terminals and having at least 50% of the butadiene unit in the polymer. Urethane reaction residue of butadiene diol,

Y is a urethane-reactive residue of a boryl compound having 3 to 4 hydroxyl groups per molecule, and

Z represents a perylene-reactive residue of the diisocyanate compound;

n represents an integer of 2 to 3. 1) a urethane unsaturated resin [A] represented by the following formula:

Or at least 60% of the urethane-based unsaturated resin [A], and the remainder is represented by the general formula:

(H ₂ C = CC-0-RUZU- Tr- YUZU-X'-,

I II

'O

^L UZUY-(-UZUR-0-CC = CH ₂ ) _B (lb)

II

• 0 R '

(Where R, R ', U, Y, Z and n represent the same pearl as above,

X, represents a urethane-reactive residue of one type of zole compound selected from the group consisting of polyether diols having a number average molecular weight of 200 to 5000, polyesterdiol and polyacryldiol. A) a mixed urethane-based unsaturated resin consisting of a urethane-based unsaturated resin [Α '] represented by the following formula: 1 mol;

General formula: R "~ ^ SH) _m (2)

,,,

R "represents an organic residue having a molecular weight of 80 to 1000,

m represents an integer of 2 to 4. )

And 0.1 to 1 mol of a polythiol compound [B] represented by the following formula: in an organic solvent, while blowing an oxygen-containing gas, while stirring and holding at a temperature of 30 to 100-c for 2 to 8 hours to carry out the reaction. Characteristic thiol group-containing polybutadiene derivative or resin containing the derivative Method for producing the composition

General formula:

(H ₂ C = CC-0-RUZU-) TYUZUX

1,11

-UZUY- -UZU- -0-CC = CH ₂ ) _n (la)

II I

0 R '

(here,

R is a divalent organic residue,

R 'is one H or one CH ₃ ,

U is a urethane bond-N-C-0—

I II

H 0,

X is a pentadiene-reactive residue of a polybutadiene diol 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 chain are composed of 1 / 2-bonds. ,

Ζ represents a urethane reactive residue of a diisocyanate compound,

η represents an integer of 2 to 3. )), The urethane-based unsaturated resin [Α];

General formula: R "" i "SH) _ra (2)

(here,

R "represents an organic residue having a molecular weight of 80 to 1000,

m represents an integer of 2 to 4. )

A polythiol compound [B] represented by the formula:

A tree containing a thiol-based polybutadiene derivative obtained by reacting 30 to 70% of the thiol groups as free thiol groups so that they remain after the reaction. A resist composition from a coating film formed by applying a UV curable resin composition obtained by blending a photopolymerization initiator to a resin composition to a substrate by a contact photographic exposure method, and

The process of performing circuit bumping by the electroless plating method

For manufacturing a circuit board, comprising:

5 In claim 4, the ultraviolet-curable resin composition comprises:

At least 60% of the resin content is the thiol group-containing polybutadiene derivative,

The remaining resin is represented by the general formula:

(Where R, R ', U, Y, Z and n have the same meaning as above,

Γ represents a pentane-reactive residue of one diol compound selected from the group consisting of polyetherdiol, polyesterdiol and polyacryldiol having a number average molecular weight of 200 to 5,000. ) Or a urethane-based unsaturated resin [A '] or

The urethane-based unsaturated resin [Α '];

A polythiol compound represented by the general formula (lb); a thiol-modified compound obtained by reacting 0.1 to 1 mol of a thiol group as a free thiol group with 30 to 70% of the thiol group remaining as a free thiol group. In a resin composition having a butadiene derivative,

It is a composition containing benzyldimethyl ketone as a photopolymerization initiator.