JPH02264257A - Novel photosetting composition - Google Patents

Abstract

PURPOSE:To improve the resistance to acids and alkalis by incorporating 5 to 500pts.wt. photopolymerizable compd. into 100pts.wt. specific functionalized polyphenylene ether resin compsn. CONSTITUTION:The functionalized polyphenylene ether resin compsn. in which bromine and allyl group are covalently bonded to the polyphenylene ether resin, the content of the bromine is <=30wt.% and the content of the allyl group defined by formula I is 0.1 to 100mol% contains 5 to 500pts.wt. photopolymerizable compd. per 100pts.wt. compsn. The image swelling at the time of development is obviated and a high resolving power is obtd.; in addition, the mechanical strength of the cured film after exposing, the adhesive strength to a substrate, and the resistance to chemicals, plating soln., etc., and particularly to alkalis are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new photocurable composition, and more particularly, it relates to a new photocurable composition that has particularly excellent acid resistance and alkali resistance, and is useful for manufacturing high-density printed wiring boards. The present invention relates to a new photocurable composition having unique properties.

[Traditional technique (nei)]

Currently, printed circuit board manufacturing methods can be roughly divided into the following three methods. In other words, there is a subtractive method in which a resist image formed on a copper-clad laminate is used as a protective film to create a predetermined circuit by etching, etc., and a resist image is formed on an insulating board and chemical copper plating is performed to create a circuit. The full additive method, which forms a pore, and the semi-additive method, which is an intermediate method between the two. Among these methods, the subtractive method is currently the mainstream, but with the technological trend of increasing substrate density and high reliability, Semi-additive and full-additive methods are rapidly attracting attention because they have the disadvantage that through-hole plating is difficult and the manufacturing process is long and complicated. On the other hand, a wide variety of photocurable compositions have been developed according to various methods, and various properties are required for use in producing printed circuit boards. These properties include not only lithography properties such as sensitivity and resolution, but also properties such as heat resistance, mechanical strength, acid resistance, and alkali resistance. Among these, electroless copper plating solution resistance, especially high alkali resistance, is important.

Conventionally, photocurable resists that can be used in additive processes, especially photocurable compositions for semi-additive processes, have not had sufficient performance, and the resist image may shift or peel off from the substrate during plating. , Also, 1,1,1-trichloroethane cannot be used as a developer,
It has problems such as low resolution and is not suitable for use.

[Problem that the invention seeks to solve]

In light of these technological trends, the present inventors have conducted extensive studies and found that electroless copper has excellent acid resistance, alkali resistance, heat resistance, and mechanical strength, and can be peeled off, especially since it has high alkali resistance. We have discovered a photocurable composition that is effective in the process of forming circuits by the plating method, and have accomplished the present invention.

[Means to solve the problem]

The present invention is a functionalized polyphenylene ether resin composition comprising a reaction product of a polyphenylene ether resin and allyl bromide, wherein bromine and allyl groups are covalently bonded to the polyphenylene ether resin, and the bromine content is 3.
5 to 500 parts by weight of a photopolymerizable compound is added to 100 parts by weight of a functionalized polyphenylene ether resin composition in which the content of allyl groups defined by the following formula is 0.1 mol % to 100 mol %. The present invention relates to a new photocurable composition characterized in that it contains parts by weight.

The polyphenylene ether resin used in the present invention is
It is expressed by the following general formula.

Q-E-J-H), (1) [wherein m is an integer of 1 or 2, J is a polyphenylene ether chain substantially composed of units represented by the following formula -a, II CI+3 Q represents a hydrogen atom when m is 1, and has two phenolic hydroxyl groups in one molecule when m is 2, and a polymerizable inert substituent at the ortho and para positions of the phenolic hydroxyl group. represents the residue of a difunctional phenol compound having Q
Representative examples include compounds represented by the following two general formulas.

(In the formula, A+ and At represent the same or different linear alkyl groups having 1 to 4 carbon atoms, and X represents an aliphatic hydrocarbon residue and substituted derivatives thereof, an aromatic hydrocarbon residue and substituted derivatives thereof , represents an aralkyl group and their substituted derivatives, oxygen, sulfur, a sulfonyl group, and a carbonyl group, two phenyl groups directly bonded to A2, and the bonding positions of 82 and X are all at the ortho and para positions of the phenolic hydroxyl group. As a specific example, H3CCH3 H3CCH3 However, X is Cl1ff 0 CH:+ o.

etc. Moreover, H is hydrogen. ] As a preferable specific example of the polyphenylene ether resin of the general formula (1) used in the present invention, poly(2,6-dimethyl-1,4-phenylene ether obtained by oxidative polymerization of 2,6-dimethylphenol alone) ), and copolymers obtained from copolymerization of 2,6-dimethylphenol and 2,3,6-trimethylphenol.

The molecular weight of the polyphenylene ether resin represented by the general formula (1) used in the present invention is not particularly limited, and ranges from low molecular weight to high molecular weight can be used. Especially.

The viscosity number (ηsp/C) value measured at a temperature of 30°C and a degree of 0.5g/a (lioo form solution) is 0.2 to 1.
Those in the range of 0 can be used satisfactorily.

Allyl bromide used in the present invention is a compound represented by the following structural formula.

C1l□=CHc■, Br The method for producing the functionalized polyphenylene ether resin composition of the present invention includes the steps of -metallation of the polyphenylene ether resin in ritual (1) with an organic metal, followed by a substitution reaction with allyl bromide. Become. Examples of organic metals include methyllithium, n-butyllithium, 5ec-butyllithium,
Examples include tert-butyllithium and phenyllithium, with n-butyllithium being particularly suitable.

This reaction can be carried out in an ether solvent such as tetrahydrofuran (hereinafter abbreviated as TIIF), 1,4-dioxane, dimethoxyethane, etc., or in the presence of cyclohexane, benzene, etc. in the presence of N,N,N'N'-tetramethylethylenediamine. , toluene, xylene, and other hydrocarbon solvents.

In experimental reactions, it is preferable to use these solvents after pretreatment such as purification and dehydration, and even if they are mixed in an appropriate proportion, one or more solvents other than those listed above may be used, which will not inhibit the reaction. A solvent may also be present. This reaction is particularly preferably carried out under an inert gas atmosphere such as nitrogen or argon.

The reaction temperature and reaction time for carrying out this reaction are not particularly limited, but for metallization reactions, the temperature is between 178°C (the freezing point of the system for those that solidify) and the boiling point of the system; More preferably -78°C (i!
For those to be solidified, the reaction is carried out between the freezing point of the system) and 50°C for a time of 1 second to 5 hours, more preferably 1 minute to 3 hours. Regarding the substitution reaction with allyl bromide, the temperature is between 178°C (the freezing point of the system for those that solidify) and the boiling point of the system, more preferably 178°C (the freezing point of the system for those that solidify). -50°C for a time of 1 second to 5 hours, more preferably 1 minute to 3 hours.

The structure and composition of the functionalized polyphenylene ether resin composition of the present invention obtained by the above-mentioned method are not precisely known, however, nuclear magnetic resonance (NMR)
It is abbreviated as. ) Spectral measurements show that the functionalized polyphenylene ether resin composition of the present invention has at least the following three properties.
It has been found that it is substantially composed of units represented by one to four types of structural formulas.

In addition, the allyl group and the bromine contained in the functionalized polyphenylene ether resin composition of the present invention are both covalently bonded to the polyphenylene ether resin skeleton, and the allyl group is substantially the same as described in (4) above. It was found from the measurement of the same NMR spectrum that bromine was substantially derived from the structure (6) above.

Supporting evidence that the allyl group and bromine are covalently bonded to the polyphenylene ether resin skeleton include purification results by Soxhlet extraction and reprecipitation in addition to NMR. That is, the functionalized polyphenylene ether resin composition of the present invention is subjected to Soxhlet extraction with a solvent that does not substantially dissolve the resin composition, such as ethanol or water.
No change in the spectrum was observed in the measurement of 11- and "C-NMI?", and no change in the bromine content was observed in the determination of bromine by the fluorescent X-ray method described below.

Further, the resin composition was completely dissolved in a solvent such as chloroform and then poured into methanol to cause reprecipitation, but similarly no change was observed in the NMR spectrum and the bromine content.

The mechanism by which the structures represented by (4) to (6) are produced in the above-mentioned reactions is currently not precisely understood. However, for example, it is possible to explain as follows.

Hay et al. Journal of Polymer
5science: PARTA-1, Volume 7, 691
(1969), poly(2,6-cymethyl-1.
We present a detailed report on the metalization of 4-phenylene ether). According to the findings, for example, poly(2,
6-cymethyl-l.

In the reaction between 4-phenylene ether) and n-butyllithium, lithiation can occur at two positions: the methyl group of the polyphenylene ether chain and the 3 and 5 positions of the phenyl group. The reaction equation is shown below.

In the early stages of the HCHzLi reaction, (7) is preferentially produced, but as the reaction time progresses, the thermodynamically more stable (8)
) is more dominant.

According to the method of the present invention, allyl bromine is now reacted with (5) as a result of the structure of (7).

It is thought that (6) and (4) are generated due to the structure of (8). That is, (7)
and allyl bromide cause a nucleophilic substitution reaction (5)
It is thought that (6) is produced by a bromine-lithium exchange reaction between (7) and allyl bromide. It is also believed that (4) is produced by a nucleophilic substitution reaction between (8) and allyl bromide.

Factors governing the amount of bromine and allyl group introduced in this reaction include reaction temperature, reaction time, type of solvent, amount of organic metal to be reacted, amount of allyl bromide, etc. Although it is possible to control the amount introduced depending on any factor, it is particularly preferable to control the amount of organic metal and add allyl bromide in an amount equal to or more than the amount of organic metal. The amount of organometallic and the amount of furyl bromide used here are based on 1 mole of phenyl group of polyphenylene ether resin.
The range of 0.001 mol to 5 mol is preferable.

Furthermore, from the above-mentioned reaction mechanism, the reaction temperature and reaction time are considered to be particularly important factors controlling the amount of bromine introduced. That is, by keeping the reaction temperature low and shortening the reaction time, it is possible to promote the production of (7) relative to (8) and increase the amount of bromine introduced. More specifically, functionalization with a high bromine content can be achieved by carrying out the reaction at the lowest possible temperature and in the shortest possible time within the range of the desired bromine and allyl group content within the above-mentioned reaction temperature and reaction time ranges. A polyphenylene ether resin composition can be obtained.

The content of bromine in the functionalized polyphenylene ether resin composition of the present invention ranges from 30% by weight or less, more preferably from 20% to 0.5% by weight based on the resin composition.
The range is 1%. Further, the content of the allyl group defined by the following formula is in the range of 0.1 mol% to 100 mol%, more preferably 0.5 mol% to 50 mol%.

If the bromine content exceeds 30% by weight, thermal stability decreases, which is not preferable. In addition, if the content of allyl group is less than 0.1 mol%, the improvement in chemical resistance after curing will be insufficient;
If it is more than 0.00 mol%, it becomes extremely brittle after curing, which is not preferable.

A method for determining the bromine content in the functionalized polyphenylene ether resin composition of the present invention includes, for example, a fluorescent X-ray method. It is also possible to decompose the resin composition with heat, acid, etc., and then quantify it using techniques such as titration and ion chromatography.

On the other hand, methods for determining the allyl group content include NMR spectroscopy, infrared absorption (hereinafter abbreviated as IR) spectroscopy, and the like.

The molecular weight of the functionalized polyphenylene ether resin composition of the present invention is not particularly limited, and ranges from low molecular weight to high molecular weight can be used. /C is 0.2
-1.0 can be used satisfactorily.

The photopolymerizable compound used in the present invention includes functional groups such as acryloyl group, methacryloyl group, vinylphenyl group, allyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, maleimide group,
It has a double bond such as a phenylmaleimide group, a vinylfuryl group, a vinylpyridyl group, a vinylimidazolyl group, an epoxy group such as a glycidyl group, and the like. Common examples of these include cinnamate esters, maleimides, phenylmaleimides, bismaleimides, or trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, Acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol triacrylate, acrylates of esters of dicarboxylic acids and diols or triols, tris(hydroxyethyl)triazine acrylate, or corresponding methacrylic esters, acrylamide, methylenebisacrylamide, N-
t-Butylacrylamide, N-t-octylacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, diacetone acrylamide, 2-methyl-3-
Acrylamides such as sulfopropylacrylamide and triacrylamide formal, or their corresponding methacrylamide, styrene, divinylbenzene, acrylonitrile, methacryloyl group, ethyl acrylate, isopropyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-ethyl Hexyl acrylate, lauryl acrylate, carpitol acrylate, ethoxy acrylate, methoxypolyethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 1,4-butylene glycol monoacrylate, Dimethylaminoethyl acrylate, diethylaminoethyl acrylate, tetrahydrofurfuryl acrylate, 2-chloroethyl acrylate, 2
．． Monoacrylates such as 3-dibromopropyl acrylate, tribromphenyl acrylate, allyl acrylate, and oleyl acrylate, as well as bentanediol, hexanediol, ethylene glycol, tetraethylene glycol, nonaethylene glycol, polyethylene glycol, neobentanediol, and polypropylene glycol. , acrylic esters or methacrylic esters of diols such as neobentanediol ester of adipic acid, but are not particularly limited thereto.

For example, monomers such as glycidyl methacrylate and styrene, polyfunctional monomers having a styrene skeleton, or reactive functional groups such as epoxy resins,
In addition, as long as it is photopolymerizable, it can be used as a photopolymerizable compound in the photocurable layer of the present invention, and it may be either liquid or solid at room temperature.

The photopolymerizable compound that can be used in the present invention does not need to be one type, and the above-mentioned compounds can be used in combination.

The amount of the photopolymerizable compound of the present invention used is 5 to 5 parts by weight based on 100 parts by weight of the functionalized polyphenylene ether resin composition.
00 parts by weight is common, and from the viewpoint of sensitivity of the photocurable layer, 2 parts by weight.
The amount is preferably 0 parts by weight or more, and from the viewpoint of resolution, the preferable range is 250 parts by weight or less. Further, from the overall viewpoint of the photocurable composition of the present invention, a particularly preferable range is 30 to 250 parts by weight.

In order to make the photocurable composition of the present invention more effective, it can contain the following thermoplastic resins. The content ratio of this thermoplastic resin is 10 to 100 parts by weight based on 100 parts by weight of the functionalized polyphenylene ether resin composition.
It is generally 0 parts by weight, and preferably 15 to 800 parts by weight from the viewpoint of sensitivity as a photocurable composition. Examples of thermoplastic resins that can be used include vinyl polymers such as polymethyl methacrylate, methyl methacrylate copolymer, polystyrene, styrene copolymer, polyvinyl chloride, vinyl chloride copolymer, polyvinyl acetate, and vinyl acetate copolymer. Examples include polymers, polyvinyl alcohol, and cellulose derivatives. When halogenated hydrocarbons are used as the developing liquid among these thermoplastic resins, polymethyl methacrylate or methyl methacrylate copolymer or a mixture thereof, polystyrene or styrene copolymer or a mixture thereof are particularly preferred. preferable.

In the present invention, it is preferable to add a photopolymerization initiator and a photosensitizer for the purpose of shortening reaction time and curing time. The amount of this photopolymerization initiator added is 30% by weight or less, preferably 0.01 to 20% by weight in the photocurable composition. Usable photoinitiators or photosensitizers include, for example, benzoin, benzoin alkyl ether, polynuclear quinones such as anthraquinone, benzophenone, clobenzophenone, Michler's ketone, freonone, thioxanthone, dialkylthioxanthone, halogenated thioxanthone, naphthalenesulfonyl chloride. , azobisisobutyronitrile, 1-azobis-1cyclohexanecarbonitrile, 2,4-dichlorobenzoyl peroxide, diphenyl disulfide, dibenzothiazole, 1-
(4-isopropylphenyl)-2-hydroxy-2-
Methylpropan-1-one, 2-hydroxy-2-methyl l-phenylpropan-1-one; dyes, electrons and donor substances such as erythrosine, triethylamine, p-amine benzoic acid esters, triphenylphosphine, 2.
Examples include 2-dimethoxy-2-phenylacetophenone. These photopolymerization initiators or photosensitizers may be used alone or in combination of two or more.

Furthermore, additives such as dyes, stabilizers, and plasticizers can be added to the photocurable composition of the present invention, if necessary.

〔Effect of the invention〕

The photocurable composition of the present invention has high resolution without image swelling during development, and has particular properties such as mechanical strength of the cured film after exposure, adhesion to the substrate, chemical resistance, and plating liquid resistance. Excellent alkali resistance. In addition, it has excellent performance in both the copper through-hole method and the solder through-hole method, and it is said that using this method makes it easy to create high-density, high-precision printed circuit boards, and also simplifies the printed circuit board manufacturing process. There are advantages.

It is particularly effective in the process of forming a circuit by an electroless plating method, and one preferred embodiment of forming a circuit using the photocurable composition of the present invention is to apply the photocurable composition on a substrate. After laminating, exposing and developing a desired pattern using high-energy radiation, copper plating is performed using an electroless copper plating solution. . There is an example in which a resist image formed on the substrate is then peeled off to create a predetermined circuit.

The high-energy rays mentioned here include ultraviolet light, deep ultraviolet light, laser light, etc. that can efficiently cure the photocurable layer, and soft X-rays, electron beams, etc. can also be used in the photocurable layer of the present invention. Effective for curing.

〔Example〕

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

The analytical apparatuses and analytical methods used in the following synthesis examples and examples are as follows.

・Viscosity number ηsp/C: Temperature 30'C, 0.5g/d1
Chloroform solution / Bromine content: Fluorescent X-ray / Allyl group content: Nuclear magnetic resonance spectrum / Fluorescent X-ray: Rigaku Denki Kogyo, 3064-M type / NMR (nuclear magnetic resonance spectrum): JCOL, JMR-GX 400
Measured value by type ET-NMR (400MHz).

Poly(2,6-dimethyl-1,4-phenylene ether) having a viscosity number η sp/C of 0.55 as measured in a 30″C, 0.5 g/lU chloroform solution 10. Dissolve 0g in T)IF200d and dissolve n-butyllithium (1
, 5 mol/l, hexane solution) 11.1 mj! was added and reacted for 5 minutes at 25°C under a nitrogen atmosphere. Subsequently, 1.5 m of allyl bromide was added, and the mixture was further stirred at 25°C for 30 minutes. Finally, a mixed solution of 80ml of water and 80ml of methanol was added to precipitate the polymer. After repeating filtration and methanol washing three times, it was vacuum dried at 80°C for 14 hours to obtain a white powdery resin composition. This is called resin composition (8).

Synthesis Example 2 The reaction conditions for n-butyllithium in Synthesis Example 1 were changed to 2.
A resin composition was obtained by carrying out the reaction in the same manner as in Synthesis Example 1 except that the temperature was changed from 5°C for 15 minutes to 25°C for 115 minutes.

The obtained resin composition is referred to as resin composition (B).

Synthesis Example 3 The reaction conditions for n-butyllithium in Synthesis Example 1 were changed to 2.
A resin composition was obtained by carrying out the reaction in the same manner as in Synthesis Example 1 except that the temperature was changed from 15 minutes at 5°C to 11 hours at 40°C. The obtained resin composition is referred to as resin composition (C).

Synthesis Example 4 8.0 g of the same poly(2,6-dimethyl-1,4-phenylene ether) used in Synthesis Example 1 was added to TIIF40.
n-butyllithium (1.5 mol/l)
, hexane solution) 88.9mj! was added and reacted for 200 minutes at 25°C under a nitrogen atmosphere. followed by allyl bromide 1
1.5 mjl was added, and the mixture was further stirred at 25°C for 30 minutes. Finally, the reaction mixture was mixed with methanol 1. Of
to precipitate the polymer. After repeating filtration and methanol washing three times, it was vacuum dried at 80°C for 14 hours to obtain a white powdery resin composition. The obtained resin composition is referred to as resin composition (D).

The viscosity number, bromine content, allyl foundation, and amount of the resin compositions obtained in Synthesis Examples 1.2.3 and 4 were measured. The results are shown in Table-1.

Table 1 Examples 1 to 8 The resin composition obtained in the synthesis example, the photopolymerizable compound, the initiator, the solvent, and, if necessary, the dye were each placed in 11 separable flasks equipped with a stirrer. The mixtures were added in the proportions shown in Table 2 and stirred at 30°C for 15 hours to prepare each mixture.

Next, the mixture was applied onto a polyethylene terephthalate film having a thickness of 38 μm using a blade coater, and the film thickness was adjusted to 50 μm.
It was dried in a hot air oven at 0°C.

Furthermore, the photocurable laminate obtained above was pressed onto a copper-clad glass epoxy laminate using a 100"C pressure roll. A negative mask film was passed through the laminate using an ultra-high pressure mercury lamp (Oak Seisakusho, Phoenix 3000). Exposure was carried out using the irradiation dose shown in Table 3.
When 1.1.1-trichloroethane was sprayed using a spray nozzle for the time shown in Table 3 to dissolve and remove the unexposed areas, good images were obtained in each case.

This image (100 x 100 100am square patterns)
The pattern survival rate after the substrate on which the pattern was formed was immersed in a sodium hydroxide aqueous solution having a pH of 12 and a temperature of 80° C. for 40 hours was determined as an alkali resistance test. The results are also shown in Table 3.

Note that the images obtained in each Example had a low swelling property with respect to 1.1.1-) dichloroethane and a high resolution.

Comparative Example 1.2 Using a mixture prepared with the following composition, image formation and alkali resistance tests were conducted in the same manner as in the examples.

The results are shown in Table-3.

Konogo ± Doki Kaisoku Delpet 70 H200g Trimethylol-propane triacrylate 20g Benzophenone 8g Michler's Ketone 0.8g Guya Resin Blue P
2gMBK 30
0g stop comparison ± or dish bottom styron GP683 200g trimethylolpropane triacrylate 80g benzophenone 8g Michler's ketone 0.8 gMEK
'300g table-3

Claims (1)

[Scope of Claim] A functionalized polyphenylene ether resin composition comprising a reaction product of a polyphenylene ether resin and allyl bromide, wherein bromine and allyl groups are covalently bonded to the polyphenylene ether resin, and the bromine content is 30% by weight or less, and the content of allyl group defined by the following formula is 0
．． A photopolymerizable compound 5 is added to 100 parts by weight of a functionalized polyphenylene ether resin composition ranging from 1 mol % to 100 mol %.
A new photocurable composition characterized by containing ~500 parts by weight Allyl group content (mol%) = total number of allyl groups/total number of moles of phenyl groups x 100