WO2016184429A1

WO2016184429A1 - Pyrazoline sensitizer and preparation method and use thereof

Info

Publication number: WO2016184429A1
Application number: PCT/CN2016/082853
Authority: WO
Inventors: 钱晓春
Original assignee: 常州强力先端电子材料有限公司; 常州强力电子新材料股份有限公司
Priority date: 2015-05-21
Filing date: 2016-05-20
Publication date: 2016-11-24
Also published as: JP2018524285A; KR20170141708A; JP6774430B2; KR102061130B1

Abstract

Disclosed are a pyrazoline sensitizer and a preparation method and use thereof. The pyrazoline sensitizer has the structure as shown in formula (I) or formula (II) and absorption bands of between 350-440 nm, and is suitable for using in a light-cured system, in particular a system containing a biimidazole photoinitiator, and formula (I) and formula (II) are successive.

Description

Pyrazoline sensitizer and preparation method and application thereof

Technical field

The invention belongs to the field of organic chemistry, and particularly relates to a pyrazoline sensitizer and a preparation method thereof, and application of the sensitizer in the field of photocuring, and a photosensitive resin composition comprising the photosensitive resin A photosensitive resin laminate of the composition, a method of forming a resist pattern on a substrate using the photosensitive resin laminate, and use of the resist pattern.

Background technique

UV curing technology has been widely used due to its fast curing speed and low environmental pollution. The photoinitiator plays a decisive role in the curing efficiency of the entire curing system. In actual use, some photoinitiators do not initiate polymerization well due to the limitation of absorption wavelength, and often need to be used together with sensitizer to improve the initiation efficiency. The sensitizer is capable of continuously transferring the energy it absorbs to the photoinitiator, which is equivalent to a catalyst for photochemical reactions. However, the application of sensitizers is constrained by many factors, such as solubility, matching of absorption wavelengths, and the like. At this stage, it has been a research and development hot spot in the field to find a sensitizer that matches the absorption wavelength of the photoinitiator and has good compatibility.

The use of pyrazoline compounds as sensitizers is known, and the use of different pyrazoline compounds in photosensitive resins is disclosed, for example, in Chinese patent application CN101652715A, CN102375341A and the like. However, these conventional pyrazoline compounds have disadvantages such as unsatisfactory solubility and poor sensitivity improvement effect when used as a sensitizer.

Currently, printed wiring boards are manufactured by photolithography. The lithographic printing method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to cure and cure the exposed portion of the photosensitive resin composition, and the unexposed portion is removed by a developing solution to form a resist pattern on the substrate. After the etching or plating treatment is performed to form a conductor pattern, the resist pattern is removed from the substrate to form a conductor pattern on the substrate.

In the above photolithography method, when a photosensitive resin composition is applied onto a substrate, a method of applying a photosensitive resin composition solution (ie, a photoresist solution) on a substrate and drying it, or a substrate may be used. The upper layer is laminated with a layer composed of a support, a photosensitive resin composition (hereinafter referred to as "photosensitive resin layer"), and a photosensitive resin laminate composed of a protective layer as required (hereinafter referred to as "photosensitive dry film" "or "dry film resist") method. The latter photosensitive dry film is often used in the manufacture of printed wiring boards.

A method of manufacturing a printed wiring board using the above dry film resist will be briefly described below. First, when a protective layer of a polyethylene film or the like is provided, it is peeled off from the photosensitive resin layer. Next, the photosensitive resin layer and the support are laminated on a substrate such as a copper-clad laminate in the order of the substrate, the photosensitive resin layer, and the support using a laminator. Then, the photosensitive resin layer is exposed to ultraviolet rays such as i-rays (365 nm) emitted from an ultrahigh pressure mercury lamp by photomasking having a wiring pattern, whereby the exposed portion is polymerized and cured. The support formed of polyethylene terephthalate is then stripped. Next, the unexposed portion of the photosensitive resin layer is dissolved or dispersed by a developing solution such as a weakly alkaline aqueous solution to form a resist pattern on the substrate. Then, the formed resist pattern is subjected to a known etching treatment or pattern plating treatment as a protective mask. Finally, the resist pattern is peeled off from the substrate to produce a substrate having a conductor pattern, that is, a printed wiring board.

When a dry film resist is used, in the developing step of dissolving the unexposed portion with a weakly alkaline aqueous solution, the unpolymerized composition is dispersed in the developing solution. When these dispersions aggregate, agglomerates are formed in the developer, and when the agglomerates are generated for a long time, the frequency of filter replacement becomes high during the circulation of the developer through the filter, or the washing interval of the developing machine becomes short. Therefore, some measures have also appeared to alleviate this problem, for example, adding ethylene oxide chains to monomers or polymers. Hydrophilic groups to increase the hydrophilicity of the coacervate; attempts to reduce the agglomerates using a monomer of the indophenol type. But these do not completely solve the problem. For this reason, a novel photosensitive resin composition capable of suppressing generation of aggregates in a developer has been desired.

On the other hand, with the recent miniaturization of the printed wiring board and the expansion of the market scale, the sensitivity (to shorten the exposure time) and the resolution of the photosensitive resin composition have been proposed from the viewpoint of improving production efficiency and product quality. higher requirement.

Summary of the invention

In view of the deficiencies of the prior art, for example, low-molecular sensitizers have been basically stopped due to problems such as odor and toxicity, and the sensitizers currently used are more or less limited due to their solubility and absorption wavelength. The use thereof is limited, and the present invention provides a pyrazoline-based sensitizer and a preparation method and application thereof.

According to an aspect of the present invention, an alkenyl-containing pyrazoline-based sensitizer is provided. When applied to a photocuring system, the sensitizer is highly soluble, odorless, and has excellent effect on sensitivity improvement, and the resulting film has good resolution and adhesion. And because the molecule contains an alkenyl group, it also has a property of being difficult to migrate in use.

The alkenyl-containing pyrazoline-based sensitizer of the present invention has a structure represented by the following formula (I):

Wherein R ₁ represents a C ₁ -C ₁₀ linear or branched alkyl group, a C ₄ -C ₁₀ alkylcycloalkyl group or a cycloalkylalkyl group, a phenyl group, a substituted phenyl group, a C ₂ -C _{10 group} ; Alkenyl; R ₂ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl; R ₃ represents vacancy or -CH ₂ - CH(OH)-CH ₂ -O-, R ₃ represents a space indicating that there is no substituent between O and a benzene ring, and is directly bonded; R ₄ represents hydrogen, a C ₁ - C ₁₀ linear or branched alkyl group, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl. As a preferred embodiment, in the formula (I), R _{1 is} selected from a phenyl group, a substituted phenyl group or a C ₃ -C ₆ alkenyl group; further preferably, R _{1 is} selected from the group consisting of C ₆ H ₅ *, CH ₃ C ₆ H ₄ *, CH ₃ CH ₂ C ₆ H ₄ *, CH ₃ CH ₂ CH ₂ C ₆ H ₄ *, CH ₃ CH ₂ CH ₂ CH ₂ C ₆ H ₄ *, C ₆ H ₅ C ₆ H ₄ *, C ₆ H ₅ C ₆ H ₄ *, CH ₃ CH=CH ₂ *, CH ₃ CH ₂ CH=CH ₂ *, CH ₃ CH ₂ CH ₂ CH=CH ₂ *, (CH ₃ ) ₂ CH ₂ CH=CH ₂ *, CH ₃ CH ₂ CH ₂ CH ₂ CH=CH ₂ *, C ₆ H ₅ CH=CH ₂ *. R ₂ is preferably hydrogen, a C ₁ -C ₄ linear or branched alkyl group, more preferably hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl. R ₄ is preferably hydrogen, a C ₁ -C ₄ linear or branched alkyl group, more preferably hydrogen, methyl, ethyl, propyl or isopropyl.

The above-mentioned preference is made for the above groups, on the one hand, on the basis of ensuring the realization of the technical effects of the present application, the synthesis of the target substance is facilitated; on the other hand, the corresponding synthetic raw materials are readily available, and therefore, the preparation cost is low.

Another object of the present invention is to provide a process for producing an alkenyl-containing pyrazoline-based sensitizer having the above structure of the formula (I), comprising the steps of: (1) reacting a raw material a and a raw material b in a catalyst-containing solvent Forming intermediate a; (2) intermediate a and raw material c react under strong base to form intermediate b; (3) intermediate b is deprotected by acid to obtain intermediate c; (4) intermediate c Reaction with starting material d in glacial acetic acid at 30-100 ° C for 2-20 h to form intermediate d; (5) when R ₃ is empty: intermediate d and starting material e are reacted in a solvent containing an acid binding agent to form a product When R ₃ is -CH ₂ -CH(OH)-CH ₂ -O-: the intermediate d is reacted with epichlorohydrin in a solvent containing a phase transfer catalyst, and after the reaction is completed, a strong base is added to continue the reaction. Intermediate e; then reacting intermediate e with starting material f in the presence of a catalyst and a polymerization inhibitor to give the product;

The reaction process is as follows:

The sensitizers of the present invention are based on improvements and optimizations in the structure of the compounds. For example, the contents of the above-mentioned reaction schemes can also be found, for example, in the international patents WO 2009/060235 A and the Chinese patent CN 1515557 A, which is hereby incorporated by reference in its entirety.

Specifically, in the step (1), the solvent to be used is not particularly limited as long as it is a conventional organic reagent capable of dissolving the reaction raw materials and not participating in the reaction, such as dichloromethane, dichloroethane, toluene, benzene. , xylene, etc. The catalyst may be selected from the group consisting of methyl sulfonic acid, p-toluene sulfonic acid

The strong base described in the step (2) is potassium hydroxide, sodium hydroxide or barium hydroxide. The reaction is carried out in an organic solvent, and the type of the solvent is not particularly limited, and is generally an alcohol solvent such as methanol or ethanol. The reaction temperature and the reaction time vary depending on the structure of the raw material c. Generally, the reaction temperature is between 0 and 50 ° C and the reaction time is from 1 to 10 h.

The deprotection in the step (3) is a hydrolysis reaction process. Typically, the intermediate b can be dissolved in a hydrocarbon solvent such as dichloromethane or dichloroethane containing an acid. The acid may be concentrated hydrochloric acid, acetic acid, methanesulfonic acid or the like.

In the step (5), when R ₃ is empty, the acid binding agent is selected from the group consisting of triethylamine, potassium carbonate, ethylenediamine, pyridine, etc., and the solvent may be benzene, toluene, dichloromethane, or the like. a hydrocarbon solvent such as ethyl chloride, the reaction temperature is -10-30 ° C;

When R ₃ is -CH ₂ -CH(OH)-CH ₂ -O-, the reaction of the intermediate d with the epichlorohydrin can be carried out in a hydrocarbon solvent such as benzene, toluene or dichloroethane. The phase transfer catalyst may be selected from a quaternary ammonium salt catalyst such as tetramethylammonium bromide, tetrabutylammonium bromide or tetrapropylammonium bromide or a basic catalyst such as dimethylimidazole, and the reaction temperature is usually 10-150 ° C. . After the reaction, the strong base added is sodium hydroxide and/or potassium hydroxide. After the intermediate e is obtained, it is further reacted with the starting material f. The catalyst used in the process is triphenylphosphine, the polymerization inhibitor is p-hydroxyanisole, and the reaction temperature is 0-100 °C.

The compound represented by the above formula (I) of the present invention is odorless, has excellent solubility, and has an absorption band of between 350 and 450 nm, and is particularly suitable as a sensitizer in a photocuring system, particularly a system containing a bisimidazole photoinitiator. It has excellent effect on sensitivity improvement and the film has good resolution and adhesion. Accordingly, the present invention also relates to the use of the alkenyl-containing pyrazoline-based sensitizer in a photocurable composition.

In view of the above deficiencies in the prior art, another aspect of the present invention provides a pyrazoline sensitizer. Compared with the conventional sensitizer, the sensitizer of the invention has excellent solubility in the photocuring system, can improve the sensitivity of the photoinitiator, and has excellent resolution and adhesion.

The pyrazoline-based sensitizer of the present invention has a structure represented by the following formula (II):

among them,

R ₅ represents a substituent group having a conjugated structure with a pyrazole ring; R ₆ represents hydrogen, a C ₁ -C ₁₀ linear or branched alkyl group, a C ₄ -C ₁₀ alkylcycloalkyl group or a cycloalkyl group; alkyl; each a independently represents an -O- (CHR ₈₎ _m - of repeating units, R ₈ are each independently selected from hydrogen, methyl or ethyl, m is an integer of 1 to 6; R ₇ having n An external linkage, selected from a linear or branched alkyl group of C ₁ -C ₆₀ , optionally wherein the carbon or hydrogen may be replaced by oxygen, sulfur or a phenyl group; n represents an integer from 1 to 20.

As a preferred embodiment, in the structure represented by the above formula (I), R _{5 is} selected from a phenyl group, a pyrrolyl group, an imidazolyl group, a carbazolyl group, a fluorenyl group or an alkenyl group, and optionally, hydrogen in these groups The atoms may each be independently substituted with a C ₁ -C ₁₀ linear or branched alkyl group, a C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl group, a phenyl group, a heteroaryl group.

Further preferably, R _{5 is} selected from the group consisting of:

In the structure represented by the formula (I), R ₆ is preferably hydrogen, a C ₁ -C ₆ linear or branched alkyl group, more preferably hydrogen, methyl, ethyl, propyl, isopropyl, butyl or tert-butyl. Base, CH ₃ C(CH ₂ CH ₃ ) ₂ -.

Preferably, A is selected from the group consisting of -[O-(CHR ₈ ) _m ] _y - wherein R ₈ are each independently selected from hydrogen or methyl, m is an integer from 1 to 3, and y represents 1-9.

Further preferably, A is selected from the group consisting of -[OCH ₂ ] _y -, -[OCH ₂ CH ₂ ] _y -, -[OCH ₂ CH ₂ CH ₂ ] _y -, -[O-CH(CH ₃ ) -CH ₂ ] _y -, -[O-CH ₂ -CH(CH ₃ )-CH ₂ ] _y -, wherein y represents an integer of 1-9.

R ₇ is preferably selected from the following groups:

n is preferably an integer from 1 to 8, particularly preferably 1, 2, 3, 4, 5 and 6.

Accordingly, the present invention also relates to a process for producing a pyrazoline-based sensitizer having the structure represented by the above formula (II), comprising the steps of: (1) reacting a raw material a and a raw material b in a solvent containing a catalyst to form an intermediate (a) intermediate a and raw material c react under strong base to form intermediate b; (3) intermediate b is deprotected by acid to obtain intermediate c; (4) intermediate c and raw material d The reaction is carried out in glacial acetic acid at 30-100 ° C for 2-20 h to form intermediate d; (5) intermediate d is reacted with methyl chloroacetate under the action of an acid binding agent and a catalyst to obtain intermediate f; (6) The transesterification reaction between the body f and the starting material h under the action of the catalyst and the polymerization inhibitor gives a product; the reaction process is as follows:

Specifically, in the step (1), the solvent to be used is not particularly limited as long as it is a conventional organic reagent capable of dissolving the reaction reagent and not participating in the reaction, such as dichloromethane, dichloroethane, toluene, benzene. , xylene, etc. The catalyst may be selected from the group consisting of methyl sulfonic acid, p-toluene sulfonic acid

The deprotection in the step (3) is a hydrolysis reaction process. Typically, the intermediate b can be dissolved in a hydrocarbon solvent such as dichloromethane or dichloroethane containing an acid. The acid may be hydrochloric acid, acetic acid, methanesulfonic acid or the like.

The reaction in the step (5) is carried out in a solvent which may be acetone, DMF, acetonitrile or the like which is a conventional organic reagent capable of dissolving the reaction reagent and not participating in the reaction. The acid binding agent may be pyridine, triethylamine, potassium carbonate or the like, and the catalyst is generally potassium iodide or sodium bromide. The reaction temperature is 40-100 ° C, and the reaction time is 4-18 h.

The transesterification reaction in the step (6) is carried out in a solvent. In particular, the solvent is not particularly limited as long as it can dissolve each reaction reagent and has no adverse effect on the reaction, and toluene, benzene, xylene or the like is preferable. The catalyst is preferably a titanic acid compound, and examples thereof include 2-ethylhexyl titanate, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, and titanium. Tetrakis(2-ethylhexyl) acid or the like may be used alone or in combination of two or more. The polymerization inhibitor may be selected from the group consisting of p-hydroxyanisole, N,N-diethylhydroxylamine, hydroquinone, catechol, p-tert-butyl catechol, methylhydroquinone, and para Oxyphenol, phenothiazine, triphenylphosphine, and the like. In the transesterification reaction, the molar ratio of the intermediate e to the raw material f is preferably n:1, the amount of the catalyst used is preferably from 3 to 10 Torr of the total amount of the material, and the amount of the polymerization inhibitor is preferably the total amount of the solvent and the reaction raw materials. The amount is 3‰-10‰, the reaction temperature is 70-130 ° C, and the reaction time is 1-8 h.

The compound represented by the above formula (II) of the present invention has excellent solubility and an absorption band of between 360 and 400 nm, and is particularly suitable as a sensitizer for use in a photocuring system, particularly a system containing a bisimidazole photoinitiator. The sensitivity is improved, and the resulting film has good resolution and adhesion. Accordingly, the present invention also relates to the use of the pyrazoline sensitizer in a photocurable composition.

According to still another aspect of the present application, there is further provided a photosensitive resin composition comprising the following components: (A) a binder polymer; (B) a photopolymerizable compound having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) a sensitizing dye; the sensitizing dye as the component (D) contains a pyrazoline compound, and the pyrazoline compound is a sensitizer of any of the above. Since the compound represented by the formula (I) or the formula (II) is excellent in solubility, when used in combination with a binder polymer, a photopolymerizable compound having at least one ethylenically unsaturated bond, and a photopolymerization initiator, A good dispersing effect can be formed with each component, the action of each component can be fully exerted, the sensitivity of the photosensitive resin composition can be improved, and the resolution and adhesion of the film structure formed from the composition can be improved.

Further, the binder polymer as the component (A) is selected from the group consisting of an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, and a phenol resin. One or more of them.

Further, in the above (A) binder polymer, the structural unit content of the polymerizable monomer having a carboxyl group is from 12 to 50% by mass.

Further, the above component (B) contains a (meth) acrylate compound having a skeleton derived from dipentaerythritol.

Further, the above (meth) acrylate compound having a skeleton derived from dipentaerythritol has a structure represented by the general formula (1):

In the formula (1), in the formula (1), R ₉ each independently represents a hydrogen atom or a methyl group, and A each independently represents a C ₂ -C ₆ alkylene group, and n is an integer of 0-20.

The present application also provides an application of the above-mentioned photosensitive resin composition for producing a photosensitive element and a laminate, an application of the above-mentioned photosensitive resin composition in producing a resist pattern, and a combination of the above-mentioned photosensitive resin The application of the material in the production of printed circuit boards and lead frames.

The present invention also relates to a photosensitive resin laminate including the above-described photosensitive resin composition, a method of forming a resist pattern on a substrate using the photosensitive resin laminate, and use of the resist pattern. The photosensitive resin composition of the present invention can exhibit very excellent performance in application by selection of a component formulation.

According to the technical solution of the present invention, since the alkenyl group and the macromolecular group are introduced in the formula (I) or the formula (II), the corresponding compound is excellent in solubility, and has an absorption band between 360 and 400 nm, which is particularly suitable. The use as a sensitizer in a photocuring system, particularly a system containing a bisimidazole photoinitiator, is excellent in sensitivity improvement, and the resulting film has excellent resolution and adhesion. And because the molecule contains an alkenyl group or a macromolecular compound, it also has a property of being difficult to migrate in use.

detailed description

It should be noted that the embodiments in the present application and the features in the embodiments may be combined with each other without conflict. The invention will be described in detail below with reference to the embodiments.

Each component used in the photosensitive resin composition of the present invention will be described in further detail below.

[(A) Binder Polymer]

Examples of the component (A) used in the present invention include an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, and an alkyd resin. And phenolic resin. From the standpoint of alkali developability, an acrylic resin is preferred. The above resins may be used singly or in combination of two or more.

(A) The binder polymer can be obtained by subjecting a polymerizable monomer to radical polymerization. Examples of the polymerizable monomer include a polymerizable styrene derivative substituted with an α-position or an aromatic ring such as styrene, vinyltoluene or α-methylstyrene, and propylene such as diacetone acrylamide. Esters of vinyl alcohols such as amide, acrylonitrile, vinyl-n-butyl ether, alkyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (methyl) Dimethylaminoethyl acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, (meth)acrylic acid -2,2,3,3-tetrafluoropropyl ester, (meth)acrylic acid, α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid Such as acrylic monomer, maleic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monoisopropyl ester and other maleic acid monoester, fumaric acid, cinnamic acid, α-cyanocinnamic acid, Kang acid, crotonic acid and propiolic acid. These may be used alone or in combination of two or more.

The (meth)acrylic acid alkyl ester may, for example, be a compound represented by the following formula, and the alkyl group in these compounds may be optionally substituted with a group such as a hydroxyl group, an epoxy group or a halogen group.

H ₂ C=C(R ₁₀ )-COOR ₁₁

In the formula, R ₁₀ represents a hydrogen atom or a methyl group, and R ₁₁ represents an alkyl group having 1 to 12 carbon atoms.

Examples of the monomer represented by the above formula include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (methyl). Amyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, ( Ethyl methacrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate and benzyl (meth)acrylate. These may be used alone or in combination of two or more.

Further, from the standpoint of alkali developability, the binder polymer as the component (A) in the present invention preferably contains a carboxyl group, for example, by allowing a polymerizable monomer having a carboxyl group and other polymerizable monomers to be free It is produced by polymerization. As the polymerizable monomer having a carboxyl group, (meth)acrylic acid and an ester thereof are preferable, and among them, methacrylic acid and an ester thereof are more preferable.

From the standpoint of the balance between alkali developability and alkali resistance, the carboxyl group content (the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomer used) of the (A) binder polymer is preferably 12- 50% by mass, more preferably 12 to 40% by mass, still more preferably 15 to 35% by mass, particularly preferably 15 to 30% by mass. When the carboxyl group content is 12% by mass or more, the alkali developability is improved, and when it is 50% by mass or less, the alkalinity tends to be excellent.

Further, the content of the structural unit derived from the polymerizable monomer having a carboxyl group in the above (A) binder polymer is related to the ratio of the carboxyl group-containing monomer, and therefore it is preferably 12 to 50% by mass, and more preferably 12 -40% by mass, further preferably 15 to 35% by mass, particularly preferably 15 to 30% by mass.

Further, the binder polymer as the component (A) in the present invention preferably contains a styrene or a styrene derivative as a polymerizable monomer from the standpoint of adhesion and chemical resistance. The above styrene or styrene derivative is copolymerized In terms of time sharing, the content (the ratio of styrene or styrene derivative to all polymerizable monomers used) is preferably from 10 to 60% by mass, more preferably from the standpoint of good adhesion and chemical resistance. Contains 15-50% by mass. When the content is 10% by mass or more, the adhesion tends to be improved, and when the content is 60% by mass or less, the time required for peeling due to the increase in the glass bottle release sheet can be suppressed.

Further, the content of the structural unit derived from styrene or a styrene derivative in the above (A) binder polymer is related to the above ratio of the styrene or styrene derivative, and is preferably from 10 to 60% by mass, more preferably It is 15-50% by mass.

These binder polymers may be used singly or in combination of two or more. When the binder polymer used in combination of two or more types is used, for example, two or more kinds of binder polymers composed of different copolymer components and two or more kinds of binder polymers having different degrees of dispersion may be mentioned. .

The above (A) binder polymer can be produced by a conventional method. in particular. For example, it can be produced by radically polymerizing an alkyl (meth)acrylate with (meth)acrylic acid, styrene or the like.

The weight average molecular weight of the above (A) binder polymer is preferably from 20,000 to 300,000, more preferably from 40,000 to 150,000, further preferably from 40,000 to 120,000, particularly preferably from 50,000 to 80,000, from the standpoint of balance of mechanical strength and alkali developability. . The weight average molecular weight in the present invention is a value obtained by conversion by a gel permeation chromatography and converted from a calibration curve prepared using standard polystyrene.

With respect to the content of the above (A) binder polymer, it is preferably 30-80 parts by mass, more preferably 40-75 parts by mass, based on 100 parts by mass of the total of the components (A) and (B), further. It is preferably 50-70 parts by mass. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured product are more excellent.

[(B) Photopolymerizable compound having at least one ethylenically unsaturated bond]

The component (B) used in the present invention is a photopolymerizable compound having at least one ethylenically unsaturated bond, at least containing a skeleton derived from dipentaerythritol, from the standpoint of improving the resolution and the reliability of the cap hole. (Meth) acrylate compound. Here, the (meth) acrylate having a skeleton derived from dipentaerythritol means an esterified product of dipentaerythritol and (meth)acrylic acid and is defined as a compound having an alkylene group modified in the esterified product. Further, the number of ester bonds in a single molecule is preferably 6, and a compound having a number of ester bonds of 1-5 may be mixed.

The (meth) acrylate having a skeleton derived from dipentaerythritol, for example, a compound represented by the following formula (1) is more specifically mentioned.

In the formula (1), R ₉ each independently represents a hydrogen atom or a methyl group, and A each independently represents a C ₂ -C ₆ alkylene group, and n is an integer of 0-20.

From the viewpoint of further improving sensitivity, adhesion, and resolution, R _{9 in the} formula (1) is preferably a methyl group. n is preferably from 0 to 15, more preferably from 0 to 10, still more preferably from 0 to 5.

Further, from the standpoint of the balance of the reliability and the clearness of the cover hole, the above (meth) acrylate having a skeleton derived from dipentaerythritol with respect to the total amount of 100 parts by mass of the components (A) and (B) The content of the compound is preferably from 3 to 25 parts by mass, more preferably from 5 to 20 parts by mass.

In addition to the above (meth) acrylate compound having a skeleton derived from dipentaerythritol, the component (B) may further contain other photopolymerizable compounds.

Examples of the other photopolymerizable compound include a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol A-based (meth) acrylate compound, and a urethane bond ( A urethane monomer such as a methyl acrylate compound, a nonylphenoxytetraethyleneoxy (meth) acrylate, a nonyl phenoxy octaethoxy ethoxy (meth) acrylate, γ- Chloro-β-hydroxypropyl-β'-(meth)acrylamide ethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalic acid Acid ester, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate and methacrylate. These may be used alone or in combination of two or more.

Among the above compounds, a bisphenol A-based (meth) acrylate compound is preferably contained from the viewpoint of improving the reliability of the cap hole and the image clarity. Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane and 2,2-bis (4). -((Meth)acryloyloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolybutoxy)phenylpropane, 2,2-double (4-((meth)acryloyloxypolyethoxypolypropoxy)phenyl)propane, etc. These may be used individually or in combination of 2 or more types.

The content of the bisphenol A-based (meth) acrylate compound is preferably 5 to 25% by mass, and more preferably 7 to 15% by mass based on the total amount of the components (A) and (B).

Examples of the compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol include polyethylene glycol di(meth)acrylate having a number of ethylene groups of 2 to 14 and a propylene group. a polypropylene glycol di(meth)acrylate having a number of 2-14, a polyethylene glycol polypropylene glycol di(meth)acrylate having a number of ethylene groups of 2 to 14 and a number of propylene groups of 2 to 14, Trimethylolpropane polyethylene tri(meth)acrylate having a number of ethylene groups of 1 to 21, tetramethylolmethane polyethylene tri(meth)acrylate having a number of 1 to 2 ethylene groups, And tetramethylolmethane polyethylene tetra(meth)acrylate having a number of ethylene groups of 1 to 30. These may be used alone or in combination of two or more.

Among the above, from the viewpoint of excellent cover hole reliability and resolution, trimethylolpropane polyethylene tri(meth)acrylate having a number of ethylene groups of 1 to 21 is preferable.

The content of the compound obtained by reacting the α,β-unsaturated carboxylic acid with the polyol is preferably from 5 to 25% by mass, more preferably from 5 to 25% by mass based on the total amount of the components (A) and (B). 7-15% by mass.

Examples of the urethane monomer include a (meth)acrylic monomer having a hydroxyl group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, and 2,4-toluene. Addition product of diisocyanate compound such as diisocyanate and 1,6-hexamethylene diisionate, tris((meth)acryloyloxytetraethylene glycol isocyanate) hexamethylene isocyanurate , EO modified urethane di(meth) acrylate and EO, PO modified urethane di(meth) acrylate, wherein EO represents ethylene oxide, and EO modified compound has epoxy The block structure of the ethane group, PO represents propylene oxide, and the PO-modified compound has a propylene oxide group block structure.

The content of the urethane monomer having an isocyanuric acid ring skeleton is preferably 5 to 25% by mass, more preferably 7 to 15% by mass based on the total amount of the components (A) and (B). %.

The above other photopolymerizable compounds may be used singly or in combination of two or more.

The content of the component (B) is preferably 20 to 70 parts by mass, more preferably 25 to 60 parts by mass, based on 100 parts by mass of the total of the components (A) and (B), further. It is preferably set to 30 to 50 parts by mass. When the content of the component (B) is in this range, the photosensitivity and coating properties of the photosensitive resin composition are further improved.

[(C) Photopolymerization Initiator]

As the photopolymerization initiator of the component (C), benzophenone, 2-benzyl-2-dimethylamino-1-(4-morphinylphenyl)-butanone-1, 2 can be exemplified. An aromatic ketone such as methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1, or an anthracene such as an alkyl group. Benzoyl ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin, alkyl benzoin, benzil derivatives such as benzil dimethyl ketal, 2-(o-chlorophenyl) 2,4,5-triarylimidazole dimer such as -4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 9- An acridine derivative such as phenyl acridine or 1,7-(9,9'-acridinyl)heptane. These may be used alone or in combination of two or more.

The initiator preferably contains a 2,4,5-triarylimidazole dimer. The above 2,4,5-triarylimidazole dimer may, for example, be 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, 2, 2',5-Tris(2-fluorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-imidazole dimer, 2 , 2',5-tris(2-fluorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-imidazole dimer, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-imidazole dimer, 2,2'-di(2- Fluorophenyl)-4-(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-imidazole dimer, etc. .

The content of the component (C) may be 0.01 to 30 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 1 to 7 parts by mass per 100 parts by mass of the parts (A) and (B). The portion is further preferably 2 to 6 parts by mass, particularly preferably 3 to 5 parts by mass. When the content is 0.1 part by mass or more, the photosensitivity, the resolution, and the adhesion tend to be improved, and when the amount is 10 parts by mass or less, the resist shape tends to be excellent.

[(D) sensitizing pigment]

The sensitizing dye as the component (D) contains a pyrazoline compound. By using in combination with a (meth) acrylate compound having a skeleton derived from dipentaerythritol as a photopolymerizable compound, it is possible to obtain a lid hole reliability, adhesion, and formation of a resist film which is excellent in photosensitivity. A photosensitive resin composition excellent in resolution of a resist pattern.

Examples of the pyrazoline compound used as the sensitizing dye include compounds having a structure represented by the formula (I) and the formula (II):

In formula (I),

R ₁ represents a C ₁ -C ₁₀ linear or branched alkyl group, a C ₄ -C ₁₀ alkylcycloalkyl group or a cycloalkylalkyl group, a phenyl group, a substituted phenyl group, a C ₂ -C ₁₀ alkene group. R ₂ represents hydrogen, a C ₁ -C ₁₀ linear or branched alkyl group, a C ₄ -C ₁₀ alkylcycloalkyl group or a cycloalkylalkyl group; R ₃ represents an empty or -CH ₂ -CH ( OH)-CH ₂ -O-; R ₄ represents hydrogen, a C ₁ -C ₁₀ linear or branched alkyl group, a C ₄ -C ₁₀ alkylcycloalkyl group or a cycloalkylalkyl group.

In formula (II),

Further information on the compounds of the above formulae (I) and (II) can be found in the Chinese Patent Application Nos. 201510264670.9 and 201510263189.8, respectively, each of which is incorporated herein by reference in its entirety.

In the component (D) sensitizing dye, the content of the compound represented by the above formula (I) and formula (II) is preferably from 10 to 100% by mass, more preferably from 30 to 100% by mass, particularly preferably 50- 100% by mass. When the content is 10% by mass or more, the sensitivity tends to be high and the resolution tends to be high.

The content of the component (D) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, more preferably 0.05 to 5 parts by mass, more preferably 100 parts by mass of the total of the components (A) and (B). It is set to 0.1 to 3 parts by mass. When the content is 0.01 parts by mass or more, the light sensitivity and the resolution tend to be easily obtained, and when it is 10 parts by mass or less, it tends to be easy to obtain a sufficiently good resist shape.

[Other components]

The photosensitive resin composition of the present invention may further contain a dye such as malachite green, Victoria pure blue, bright green or methyl violet, tribromophenylsulfone, colorless crystal violet, diphenylamine, benzylamine or triphenylamine, as needed. , photo-chromic reagents such as diethyl aniline, o-chloroaniline and tert-butyl catechol, thermal coloring inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, defoamers, flame retardants, dense A combination imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, a polymerization inhibitor, and the like. These may be used alone or in combination of two or more. Each of the additional auxiliary agents may be 0.01 to 20 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B).

The photosensitive resin composition of the present invention may contain at least one organic solvent as needed. As the organic solvent, a commonly used organic solvent can be used without particular limitation. Specific examples thereof include solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, and propylene glycol monomethyl ether, or a mixed solvent thereof.

For example, the above components (A) to (D) may be dissolved in an organic solvent to form a coating liquid. The solid content is preferably about 30 to 60% by mass, and the solid content is a component remaining after removing volatile components from the solution.

The coating liquid is applied onto the surface of a support such as a support film or a metal plate to be described later and dried, whereby a photosensitive resin layer derived from the photosensitive resin composition can be formed on the support.

Examples of the metal plate include iron-based alloys such as copper, copper-based alloys, nickel, chromium, iron, and stainless steel, and copper, copper-based alloys, and iron-based alloys are preferable.

The thickness of the photosensitive resin layer to be formed varies depending on the use thereof, but is preferably about 1-100 μm in terms of the thickness after drying. The other side of the photosensitive resin layer, that is, the surface opposite to the surface on which the support is placed, may be covered with a protective film. The protective film may, for example, be a polymer film such as polyethylene or polypropylene.

The photosensitive element of the present invention mainly consists of a support and a photosensitive resin layer derived from the photosensitive resin composition formed on the support, and further includes other layers such as a protective film provided as needed.

[support]

As the support, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.

The thickness of the above support (hereinafter sometimes referred to as "support film") is preferably from 1 μm to 100 μm, more preferably from 1 μm to 50 μm, still more preferably from 1 μm to 30 μm. When the thickness of the support is 1 μm or more, it is possible to suppress cracking of the support film when the support film is peeled off. Further, by setting it to 100 μm or less, the decrease in resolution can be suppressed.

[protective film]

The photosensitive element may further include a protective film covering the other side of the photosensitive resin layer as needed.

As the protective film, the adhesive force to the photosensitive resin layer is preferably smaller than the adhesion of the support film to the photosensitive resin layer, and a film having a small fish eye is more preferable.

Here, the term "shrinkage" refers to a material, a raw material, an unmelted material, an oxidized degradation product, etc. when a film is produced by tear melting, extrusion, biaxial stretching, casting, or the like by heat-melting a material constituting a protective film. It is included in the membrane. That is, "small shrinkage cavities" means that defects such as the above-described foreign matter in the film are small.

Specifically, as the protective film, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. Further, the protective film may be the same as the above support. The thickness of the protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, further preferably from 5 μm to 30 μm, particularly preferably from 15 μm to 30 μm. By setting the thickness of the protective film to 1 μm or more, it is possible to suppress the cracking of the protective film when the photosensitive resin layer and the support film are laminated on the substrate while peeling off the protective film. Further, by making it 100 μm or less, productivity is improved.

[Production method]

The photosensitive element of the present invention can be produced, for example, by a production method comprising the steps of: (A) a binder polymer, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D). a component such as a sensitizing dye is dissolved in an organic solvent to form a coating liquid; the coating liquid is applied onto a support to form a coating layer; and the coating layer is dried to form a photosensitive resin layer.

The coating liquid can be applied to the support by a roll coater, a ripper coater, a gravure coater, an air knife coater, a die coater, a bar coater, a spray coater, etc. A well-known method is carried out.

The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent is removed from the coating layer. For example, it can be carried out at 70-150 ° C for about 5-30 minutes. In order to prevent the diffusion of the organic solvent in the subsequent step, the amount of the residual organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less.

The thickness of the photosensitive resin layer in the photosensitive element can be appropriately selected depending on the use, and is preferably from 1 μm to 200 μm, more preferably from 5 μm to 100 μm, particularly preferably from 10 to 50 μm, in terms of the thickness after drying. When the thickness is 1 μm or more, industrial coating is easy and productivity is improved. When it is 200 μm or less, the effect of the present invention can be sufficiently obtained, the light sensitivity is high, and the photocurability of the bottom of the resist tends to be excellent.

The photosensitive element of the present invention may further have an intermediate layer such as a buffer layer, an adhesive layer, a light absorbing layer, or a gas barrier layer, etc., as needed.

The form of the photosensitive element of the present invention is not particularly limited. For example, it may be in the form of a sheet, or may be a shape wound in a series on a winding core.

When winding in a roll shape, it is preferable to wind up so that a support film may become outer side. Examples of the winding core include plastics such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, or an ABS (acrylonitrile-butadiene-styrene copolymer).

From the standpoint of protecting the end faces, it is preferable to provide the end face spacers on the end faces of the roll-shaped photosensitive element rolls thus obtained, and it is preferable to provide the moisture-proof end face spacers from the standpoint of resistance to melting. Further, as the packing method, it is preferably packaged in a black sheet having a small moisture permeability.

The photosensitive element of the present invention can be suitably used, for example, in a method for producing a resist pattern to be described later.

The method for producing a resist pattern according to the present invention includes (i) a photosensitive resin layer forming step of forming a photosensitive resin layer from the photosensitive resin composition on a substrate, and (ii) at least the photosensitive resin layer. An exposure step of irradiating the active light to partially cure the exposed portion, and (iii) a developing step of removing the uncured portion of the photosensitive resin layer from the substrate by development. Other processes may also be included as needed.

(i) Photosensitive resin layer forming process

In the photosensitive resin layer forming step, a photosensitive resin layer derived from the photosensitive resin composition is formed on a substrate. The substrate is not particularly limited, and a circuit-forming substrate having an insulating layer and a conductor layer formed on the insulating layer, or a lower pad (a substrate for a lead bar) such as an alloy substrate can be usually used.

As a method of forming a photosensitive resin layer on a substrate, for example, when the photosensitive element has a protective film, the protective film may be removed, and then the photosensitive resin layer of the photosensitive element may be crimped to the circuit while being heated. On the substrate for formation. Thereby, a laminate including the circuit-forming substrate, the photosensitive resin layer, and the support in this order is obtained.

From the standpoint of adhesion and followability, the photosensitive resin layer forming step is preferably carried out under reduced pressure. The heating at the time of crimping is preferably carried out at a temperature of 70 to 130 °C. Further, the pressure bonding is preferably carried out at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf/cm ² ). These conditions can be appropriately selected as needed. In addition, when the photosensitive resin layer is heated to 70 to 130 ° C, it is not necessary to preheat the substrate for circuit formation in advance, but in order to further improve adhesion and followability, preheating of the substrate for circuit formation may be performed. deal with.

(ii) Exposure process

In the exposure step, at least a part of the photosensitive resin layer formed on the substrate is irradiated with active light, and the exposed portion irradiated with the active light is photocured to form a latent image.

In this case, when the support (support film) present on the photosensitive resin layer is transparent to the active light, the active light can be transmitted through the support film, and when the support film is light-shielding, the support is removed. The photosensitive resin layer is irradiated with active light rays after the film.

As the exposure method, a method (mask exposure method) in which active light is irradiated in an image form via a negative or positive mask pattern called a drawing (ART WORK) is exemplified. Further, a method in which the active light is irradiated in an image form by direct drawing exposure such as LDI (Laser Direct Imaging) exposure method or DLP (Digital Light Processing) exposure method may be employed.

As a light source of the active light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure lamp, a high pressure lamp, a xenon lamp, an argon laser gas laser, a solid laser such as a YAG laser, a semiconductor laser, and a gallium nitride system are used. A source of ultraviolet light, such as a blue-violet laser. Further, a light source that efficiently emits visible light, such as a photographic floodlight or a fluorescent lamp, can also be used.

The photosensitive resin composition of the present invention is not particularly limited to the type of the light source of the active light, and a direct drawing exposure method is preferably employed.

(iii) development process

In the developing step, the uncured portion of the photosensitive resin layer is removed from the substrate by development, whereby a resist pattern composed of the cured product photocured by the photosensitive resin layer is formed on the substrate.

When the support film is present on the photosensitive resin layer, after the support film is removed, the unexposed portion other than the exposed portion is removed (developed). Development methods include wet development and dry development.

In the case of wet development, development is carried out by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the development method include a method using an immersion method, a stirring method, a spraying method, a brushing method, a tapping method, a doctor coating method, and a shaking immersion, and a high-pressure spray method is most suitable from the viewpoint of improving the resolution. It is also possible to develop two or more of the above methods in combination.

The configuration of the developer can be appropriately selected depending on the configuration of the photosensitive resin composition. For example, an alkaline aqueous solution, an aqueous developing solution, and an organic solvent-based developing solution can be mentioned.

When an alkaline aqueous solution is used as a developing solution, it is safe and stable, and the workability is also good. As the base in the alkaline aqueous solution, for example, an alkali hydroxide such as a hydroxide of lithium, sodium or potassium, a carbonate such as lithium, sodium, potassium or ammonia or a carbonate such as hydrogencarbonate, a phosphate base, a sodium phosphate or the like can be used. An alkali metal pyrophosphate such as an alkali metal phosphate, sodium pyrophosphate or potassium pyrophosphate.

As the alkaline aqueous solution used for development, a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of sodium carbonate, a solution of 0.1 to 5 % by mass of sodium hydroxide, and a solution of 0.1 to 5 % by mass of sodium tetraborate are preferable. Wait. Further, the pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature thereof can be adjusted according to the developability of the photosensitive resin layer. Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

The aqueous developing solution is, for example, a developing solution composed of water or an alkaline aqueous solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, in addition to the above, for example, borax, sodium silicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino- 2-Hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2 and morphine. The pH of the aqueous developing solution is preferably as small as possible within a range capable of sufficient development, and is preferably pH 8-12, more preferably pH 9-10.

Examples of the organic solvent used in the aqueous developing solution include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, and butanol. , diethylene glycol monomethyl ester, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether. These may be used alone or in combination of two or more. The concentration of the organic solvent in the aqueous developing solution is usually preferably from 2 to 90% by mass, and the concentration thereof can be adjusted in accordance with developability. A surfactant, an antifoaming agent, or the like may be mixed in a small amount in the aqueous developing solution.

Examples of the organic solvent-based developing solution include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-. Butyrolactone. In order to prevent ignition, it is preferred to add water in the range of 1 to 20% by mass in these organic solvents.

In the present invention, after the unexposed portion is removed in the developing step, the resist pattern may be further cured by heating at about 60 to 250 ° C or exposure at about 0.2 to 10 J/cm ² as needed.

A method of manufacturing a printed wiring board according to the present invention includes a step of forming a conductor pattern by performing an etching treatment or a plating treatment on a circuit formation substrate on which a resist pattern is formed. Other steps such as a resist removal step are also included as needed. The photosensitive resin composition of the present invention can be suitably used for the production of a resist pattern, and is more suitably used for a method of producing a conductor pattern by a plating process.

In the etching process, a conductor pattern of a circuit formation substrate which is not covered with a resist is etched away by using a resist pattern formed on a substrate as a mask to form a conductor pattern.

The etching treatment method can be appropriately selected depending on the conductor layer to be removed. For example, examples of the etching solution include a copper oxide solution, an iron oxide solution, an alkali etching solution, and a hydrogen peroxide-based etching liquid.

On the other hand, in the plating process, copper, solder, or the like is plated on the conductor layer of the circuit-forming substrate which is not covered with the resist, using the resist pattern formed on the substrate as a mask. After the plating treatment, the cured resist is removed, and the conductor layer covered with the resist is etched to form a conductor pattern.

As a method of the plating treatment, it may be a plating treatment or an electroless plating treatment, and an electroless plating treatment is preferred. Examples of the electroless plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw soldering, and Watt bath (nickel sulfate-chlorination). Gold plating such as nickel plating, hard gold plating, and soft gold plating such as nickel plating and nickel sulfamate plating.

After the etching treatment or the plating treatment, the resist pattern on the substrate is removed. The removal of the resist pattern can be carried out, for example, by an aqueous solution which is more alkaline than the alkaline aqueous solution used in the development step described above. As the strongly alkaline aqueous solution, for example, a 1-10% by mass aqueous sodium hydroxide solution can be used, and a 1-5% by mass aqueous sodium hydroxide solution is preferably used.

Examples of the method of peeling off the resist pattern include a dipping method and a spraying method, and these may be used singly or in combination.

When the resist pattern is removed after the plating treatment is performed, the conductor layer covered with the resist may be etched by an etching process to form a conductor pattern, whereby a desired printed wiring board can be manufactured. The method of the etching treatment at this time can be appropriately selected depending on the conductor layer to be removed. For example, the above etching liquid can be applied.

The printed wiring board manufactured by the method for manufacturing a printed wiring board according to the present invention can be applied not only to the manufacture of a single-layer printed wiring board but also to the manufacture of a multilayer printed wiring board, and can also be applied to a small-sized printed wiring board. Manufacturing of printed wiring boards and the like of through-holes.

A method of manufacturing a lead frame according to the present invention includes a step of forming a conductor pattern by plating a substrate on which a resist pattern is formed. Other steps such as a resist removal step and an etching treatment step are also included as needed.

As the substrate, a backing plate (base material for a lead frame) such as an alloy substrate is used as the substrate. In the present invention, a plating process is performed on a substrate by using a resist pattern formed on a substrate as a mask.

As a method of a plating process, the method demonstrated by the manufacturing method of the said printed wiring board is mentioned. After the plating treatment described above, the resist pattern on the substrate is removed. The removal of the resist pattern can be carried out, for example, by an aqueous solution which is more alkaline than the alkaline aqueous solution used in the development step described above. Examples of the strongly alkaline aqueous solution include the aqueous solutions described in the above-described method for producing a printed wiring board.

Examples of the peeling method of the resist pattern include a dipping method, a spraying method, and the like, and these may be used singly or in combination. After the resist pattern is removed, an unnecessary etching process is performed to remove an unnecessary metal layer, whereby a lead frame can be manufactured.

The beneficial effects of the present application will be further clarified by the following examples and comparative examples. The following examples are merely illustrative of the embodiments of the present application and should not be used as a basis for limiting the scope of the claims.

Example 1

(1) To a 1000 mL four-necked flask, 183 g of p-hydroxybenzaldehyde, 5 g of catalyst p-toluenesulfonic acid pyridinium salt, 300 mL of dichloromethane, and 126 g of dihydropyran were added dropwise at a temperature of 50 ° C, and the dropwise addition time was about 1 h. Stirring was continued for 10 h, the liquid phase was followed until the reaction was stopped without changing, and then the dichloromethane was removed by rotary evaporation to obtain 275 g of Intermediate 1a, which was used in the next step.

(2) Add 247g of intermediate 1a, 144g of acetophenone, and 300mL of methanol to a 1000mL four-necked flask. Stir at room temperature in a water bath, add 80g of 40% sodium hydroxide solution dropwise within 2h, then continue stirring for 6h. No change, filtration, methanol recrystallization, drying to obtain 330g of solid, ie intermediate 1b, purity 93%;

(3) Into a 1000 mL four-necked flask was added 165 g of intermediate 1b, 30 g of 37% concentrated hydrochloric acid, 500 mL of dichloromethane, stirred at room temperature for 5 h, filtered, rinsed with methanol, and dried to obtain 120 g of intermediate 1c, purity 98%;

(4) To a 1000 mL four-necked flask, 112 g of intermediate 1c and 500 g of glacial acetic acid were added, and the mixture was heated to 50 ° C with stirring, 108 g of phenylhydrazine was added dropwise, and the addition was completed in about 2 h, and then the reaction was continued for 8 h, filtered, and recrystallized from methanol to give 118 g. Body 1d, purity 98%;

(5) To a 250 mL four-necked flask was added Intermediate 1d (31.4g, 0.1mol), triethylamine (12.1g, 0.12mol), dichloromethane (30mL), and the temperature was controlled at 0 °C in an ice water bath. Acryloyl chloride (9.05g, 0.1mol) was added dropwise with stirring. The reaction was stopped in the liquid phase until the reaction was completed. The reaction was stopped, poured into 150 mL of water and stirred. The aqueous layer was extracted with dichloromethane, and the methylene chloride layer was evaporated. 36.3 g of product 1 was obtained, the yield was 99.5%, and the HPLC purity was 99%. The reaction formula of the step (5) is as follows.

The structure of the product 1 was confirmed by ¹ H-NMR.

¹ H-NMR (CDCl ₃ , 500 MHz): 1.9048 (1H, s), 1.9437 (1H, s), 5.5099-5.7629 (2H, d), 6.4071-26.2221 (2H, d), 7.0309-7.1198 (3H, m ), 7.3067-7.6319 (5H, m).

Example 2

Intermediate 1d (94.3 g, 0.3 mol), toluene (50 mL), epichlorohydrin (27.8 g, 0.3 mol), tetrabutylammonium bromide (0.5 g), and temperature control 70 were added to a 500 mL four-necked flask. The reaction was carried out for about 5 h at °C, the liquid phase was traced to completion, then cooled to room temperature, 20 g of sodium hydroxide was added, and the temperature was controlled at 30 ° C for 3 h, and the liquid phase was followed. The reaction was completed to completion, then 100 mL of water was added and stirred, the aqueous layer was extracted with toluene, and the toluene layer was combined and evaporated to give 106.6 g of product intermediate e.

Take intermediate e (37.0g), methacrylic acid (8.6g, 0.1mol), toluene (30mL), triphenylphosphine (0.1g), p-hydroxyanisole (0.1g), react at 110 ° C for 5h, reaction After completion, the temperature was lowered to room temperature, the toluene layer was washed with water, the toluene product solution was rotaryly evaporated, and methanol was recrystallized to obtain 41.6 g of product 2, yield 88%, purity 99%.

The structure of the product 2 was confirmed by ¹ H-NMR.

¹ H-NMR (CDCl ₃ , 500 MHz): 1.9122-2.0309 (6H, s), 4.0887-4.3425 (5H, d), 5.5909 (1H, s), 6.1125 (1H, s), 6.4702-6.7221 (5H, m ), 7.0309-7.3067 (7H, m), 7.5927-7.6651 (2H, t).

Example 3-14

The product 3-14 having the structure shown below was synthesized by the method of Example 1 or 2:

Example 15

(1) Preparation of intermediate a:

183 g of p-hydroxybenzaldehyde, 5 g of catalyst p-toluenesulfonic acid pyridinium salt, 300 mL of dichloromethane were added to a 1000 mL four-necked flask, and 126 g of dihydropyran was added dropwise at a temperature of 50 ° C. The dropping time was about 1 h, and the addition was continued. After stirring for 10 h, the liquid phase was followed until the reaction was stopped without changing, and then dichloromethane was removed by rotary evaporation to obtain 275 g of intermediate a, purity 98%, which was directly used for the next reaction;

(2) Preparation of intermediate 1b:

To a 1000 mL four-necked flask was added 247 g of intermediate a, raw material c, 235 g of diacetophenone, and 300 mL of methanol, and stirred at room temperature in a water bath. 80 g of 40% sodium hydroxide solution was added dropwise over 2 h, stirring was continued for 6 h, and the liquid phase was followed until the reaction was carried out. No change, filtration, methanol recrystallization, drying 415g solid, ie intermediate 1b, purity 93%;

(3) Preparation of intermediate 1c:

To a 1000 mL four-necked flask, 384 g of intermediate 1b, 50 g of 37% concentrated hydrochloric acid, 500 mL of dichloromethane, and stirred at room temperature for 5 h, filtered, rinsed with methanol, and solid dried to obtain 210 g of intermediate 1c, purity 98%;

(4) Preparation of intermediate 1d:

To a 1000 mL four-necked flask, 180 g of intermediate 1c and 500 g of glacial acetic acid were added, and the mixture was heated to 50 ° C with stirring, and 108 g of phenylhydrazine was added dropwise thereto, and the addition was completed in about 2 hours. Then, the reaction was continued for 8 hours, filtered, and recrystallized from methanol to obtain intermediate 1d 210 g. 98% purity;

(5) Preparation of intermediate 1e:

78 g of intermediate 1d, 3 g of potassium iodide, potassium carbonate 35 g, and acetonitrile 80 mL were placed in a 500 mL four-necked flask, and the mixture was heated under reflux at 80 ° C, and 2 g of methyl chloroacetate was added dropwise thereto, and the addition was completed in about 1 hour. After the completion of the dropwise addition, the reaction was continued for 8 hours. After completion of the reaction, the unreacted potassium carbonate was removed by hot filtration, washed with water, and the solid was precipitated, suction filtered, and recrystallized from methanol to give a pale yellow solid, intermediate 1e 76 g, purity 99%; the structure of intermediate 1e was passed through ¹ H- NMR was confirmed. ¹ H-NMR (CDCl ₃ , 500 MHz): 3.2981-3.4209 (1H, t), 3.6038 (3H, s), 4.398 (1H, d), 4.2765-4.3951 (2H, d), 4.8954 (2H, s), 6.3854-7.4809 (19H, m).

(6) Preparation of product 15:

Into a 500 mL four-necked flask, 74.6 g of Intermediate 1e, 14.3 g of raw material 1f, 0.1 g of tetraisopropyl titanate, 0.1 g of p-hydroxyanisole, and 100 mL of toluene were added, and the mixture was heated and stirred at a temperature of 90-100 ° C while heating. The methanol produced by the reaction is distilled off, and toluene is added in a timely manner until no methanol is distilled off, and the filtrate is filtered while being vacuumed, and the obtained filtrate is distilled under reduced pressure to distill off toluene to give a pale yellow viscous material of 90 g. Product 15.

Example 16

The synthesis of the intermediate 2e was carried out in accordance with Example 15. Preparation of product 16:

7.36 g of compound 2e, 27.2 g of raw material 2f (9-EO), 0.1 g of tetraisopropyl titanate, 0.1 g of p-hydroxyanisole, 100 mL of xylene, and a temperature control of 90-100 ° C were placed in a 500 mL four-necked flask. The mixture is heated and stirred, and the methanol produced by the reaction is distilled off while heating, and xylene is added in a timely manner until no methanol is distilled off, and the filtrate is filtered under reduced pressure, and the obtained filtrate is distilled under reduced pressure to distill off toluene to give a pale yellow gum. The thick material is the product 16.

Example 17-26

The products 17-26 having the following structure were synthesized by the method of Example 15:

Performance evaluation

The application properties of the sensitizers of the formula (I) and the formula (II) of the present invention were evaluated by formulating an exemplary photocurable composition (i.e., a photosensitive resin composition).

1. Preparation of performance evaluation object

<Preparation of Photosensitive Resin Laminate> A photosensitive resin composition having the composition shown in Table 1 and PGMEA (propylene glycol methyl ether acetate) were thoroughly stirred and mixed, and a 19 μm-thick polyparaphenylene as a support was applied using a rod. The surface of the ethylene glycol diester film was uniformly coated, and then dried in a dryer at 95 ° C for 4 minutes to form a photosensitive resin layer having a thickness of 40 μm.

Then, a 23 μm-thick polyethylene film which is a protective layer is bonded to the surface of the photosensitive resin layer on which the polyethylene terephthalate film is not laminated, to obtain a photosensitive resin laminate.

<Size of the substrate surface> As a substrate for sensitivity and resolution evaluation, a ketone laminate which was treated with a jet washer at a spray pressure of 0.20 MPa was prepared.

<Lamination> The polyethylene film of the photosensitive resin laminate was peeled off, and the surface was flattened, and the laminate was laminated to a ketone layer preheated to 60 ° C at a roll temperature of 105 ° C by a hot roll laminator. On the platen, the gas pressure was 0.35 MPa, and the laminating speed was 1.5 m/min.

<Exposure> The exposure was performed by an exposure amount of a stepwise exposure level of 8 in accordance with the sensitivity of the direct-drawing type exposure apparatus of the h-ray type.

<Development> After peeling off the polyethylene terephthalate film, it was sprayed with a 1% by mass aqueous sodium carbonate solution at 30° C. to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required to completely dissolve the photosensitive resin layer of the unexposed portion was taken as the minimum development time.

Table 1

Note: The names/compositions of the components indicated by the simplified symbols in Table 1 are shown in Table 2.

Table 2

2, performance evaluation method

(1) Compatibility test

The photosensitive resin composition having the composition shown in Table 1 was sufficiently stirred and mixed, and uniformly applied onto the surface of a 19 μm-thick polyethylene terephthalate film as a support using a bar coater. It was dried in a dryer at 95 ° C for 4 minutes to form a photosensitive resin layer. Thereafter, the coated surface was visually observed and classified as follows:

◇: The coated surface is uniform; ◆: Undissolved matter is precipitated on the coated surface.

(2) Odor evaluation

By evaluating the prepared photosensitive resin composition by a fanning method, the following classification was carried out:

○: no odor; ◎: odor.

(3) Sensitivity evaluation

The laminated substrate was exposed to light for 15 min using a 21-stage stage exposure meter manufactured by Stouffer, which has a 21 degree brightness change from transparent to black, to evaluate its sensitivity. After the exposure, the development time was twice as long as the minimum development time, and the exposure was performed according to the exposure amount of the staged exposure level of 8 which was completely left by the resist film, and was classified as follows:

○: The exposure amount was less than 20 mJ/cm ² ; ◎: the exposure amount was 20 mJ/cm ^{2 to} 50 mJ/cm ² (excluding the end value); ●: the exposure amount was more than 50 mJ/cm ² .

(4) Resolution evaluation

The laminated substrate is exposed for 15 minutes by a linear pattern mask having a ratio of the exposed portion and the unexposed portion having a width of 1:1, and then developed with a development time of 2 times of the minimum development time to form a cured resist normally. The minimum mask line width of the line is taken as the resolution value.

○: The resolution value is 30 μm or less; ◎: The resolution value is 30 μm to 50 μm (excluding the end value); ●: The resolution value is 50 μm or more.

(5) Adhesion evaluation

The laminated substrate was exposed to a linear pattern mask having a ratio of the exposed portion and the unexposed portion to a width of 1:100 for 15 minutes, and then developed with a development time of 2 times the minimum development time to form a cured resist normally. The minimum mask line width of the line is used as the adhesion value.

○: the adhesion value was 30 μm or less; ◎: the adhesion value was 30 μm to 50 μm (excluding the end value); ●: the adhesion value was 50 μm or more.

3. Performance evaluation results

The performance evaluation results are shown in Table 3.

table 3

Note: *1 cannot be evaluated due to dissolution on the surface of the resist;

*2 The resist is not sufficiently cured, and a resist line cannot be formed.

It can be seen from the evaluation results of Table 3 that the composition using the sensitizer of the present invention (Examples 1-5, 14-18) has good compatibility and odorlessness in the case where the other components are the same. It has high sensitivity and excellent resolution and adhesion, and is superior to Comparative Example 1-3 using the existing sensitizer. Comparative Examples 4 and 5 show that the composition does not cure at all in the case of a BCIM photoinitiator or sensitizer alone.

In summary, the compounds of the formula (I) and formula (II) of the present invention can be used as sensitizers in the field of photocuring in combination with photoinitiators, especially bisimidazole photoinitiators such as BCIM, which can exhibit excellent applications. Performance has broad application prospects.

Example of photosensitive resin composition

The invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention. In addition, “parts” and “%” are quality benchmarks unless otherwise stated.

[Examples 27-30, Comparative Examples 6-9]

Solution a was prepared by mixing 125 g of methacrylic acid as a comonomer, 275 g of methyl methacrylate and 100 g of styrene with 1.0 g of azobisisobutyronitrile.

Solution b was prepared by dissolving 1.0 g of azobisisobutyronitrile in a mixed solution of 60 g of methyl cellosolve and 40 g of toluene.

In a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube, 400 g of a mixture of methyl cellosolve and toluene having a mass ratio of 6:4 was added, and the mixture was stirred while being blown with nitrogen gas, and heated to 80 ° C.

After the above solution a was added dropwise thereto over 4 hours, the mixture was kept at 80 ° C for 2 hours while stirring. Next, the solution b was added dropwise to the solution in the flask over 10 minutes, and the solution in the flask was stirred while maintaining the temperature at 80 ° C for 3 hours. Further, the solution in the flask was heated to 90 ° C over 30 minutes, kept at 90 ° C for 2 hours, and then cooled to obtain a solution of the binder polymer (A-1).

Acetone was added to the solution of the binder polymer (A-1) to prepare a nonvolatile content (solid content) of 50% by mass.

Solution c was prepared by mixing 125 g of methacrylic acid as a comonomer, 25 g of methyl methacrylate, 125 g of benzyl methacrylate, and 225 g of styrene with 1.5 g of azobisisobutyronitrile.

A solution d was prepared by dissolving 1.2 g of azobisisobutyronitrile in a mixed solution of 60 g of the cellosolve of methyl and 40 g of toluene.

The solution c was added dropwise thereto over 4 hours, and then kept at 80 ° C for 2 hours while stirring. Next, the solution d was added dropwise to the solution in the flask over 10 minutes, and the solution in the flask was stirred while maintaining the temperature at 80 ° C for 3 hours. Further, the solution in the flask was heated to 90 ° C over 30 minutes, and the mixture was kept at 0 ° C for 2 hours, and then cooled to obtain a solution of the binder polymer (A-2).

Acetone was added to the solution of the binder polymer (A-2) to prepare a nonvolatile content (solid content) of 50% by mass.

The binder polymer (A-1) had a weight average molecular weight of 60,000 and an acid value of 163 mgKOH/g. The binder polymer (A-2) had a weight average molecular weight of 50,000 and an acid value of 163 mgKOH/g. The weight average molecular weight was determined by gel permeation chromatography and converted using a standard polystyrene calibration curve, and the conditions of GPC are shown below.

-GPC condition

Pump: Japan Shimadzu Corporation LC-20AD type; column: GPC KF-803 (Japan Shimadzu Corporation); eluent: tetrahydrofuran; measuring temperature: 25 ° C; flow rate: 1 mL / min; detector: RID-10A.

The photosensitive resin compositions of Examples 27 to 30 and Comparative Examples 6 to 9 were prepared in the proportions shown in Table 4. The values in the table indicate the number of parts (quality basis). Further, the components (A) and (B) are masses in terms of solid content.

Table 4

The components in the above table are as follows.

- (A) binder polymer -

A1: methacrylic acid/methyl methacrylate/styrene=25/55/20 (weight ratio), weight average molecular weight=60000, 50% by mass solution; A2: methacrylic acid/methyl methacrylate/methyl Benzyl acrylate/styrene = 25/5/25/45 (weight ratio), weight average molecular weight = 50000, 50% by mass solution.

- (B) Photopolymerizable compound -

B1: a compound of the formula (1) wherein n=0, R ₉ is a methyl group; B2: trimethylolpropane trimethacrylate (TMPO); B3: 2,2-bis(4-((methyl) Acryloyloxypolyethoxy)phenyl)propane; B4: ethoxylated trimethylolpropane triacrylate (ETPTA); B5: tris(methacryloyloxytetraethylene glycol isethrine Ester hexamethylene)isocyanurate.

-(C) Photopolymerization Initiator -

C1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole (BCIM).

-(D) sensitizing pigments -

D4: 4,4'-bis(diethylamino)benzophenone.

The photosensitive resin composition was uniformly applied to a polyethylene terephthalate film (manufactured by Teijin Co., Ltd., product name "HTF01") having a thickness of 16 μm, and passed through a hot air convection dryer at 100 ° C. After drying for 10 minutes, a photosensitive resin layer having a film thickness of 10 μm after drying was formed.

A protective film made of polypropylene (manufactured by Oji Paper Co., Ltd., product name E200C) was attached to the photosensitive resin layer, and a polyethylene terephthalate film (support film) and a photosensitive resin layer were laminated in this order. And photosensitive elements of the protective film.

A copper-clad laminate (a substrate, a Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which a copper foil having a thickness of 12 μm is laminated on both surfaces, using a brush having a brush equivalent to #600 (manufactured by Sanken Co., Ltd.) The copper surface of the product name "MCL-E-67" was ground, washed with water, and then dried by a stream of air. The polished copper-clad laminate was heated to 80 ° C, and the photosensitive member obtained above was laminated while peeling off the protective film so that the photosensitive resin layer contacted the copper surface. Lamination was carried out using a hot roll at 110 ° C at a pressure of 0.40 MPa and a roll speed of 1.5 m/min.

Thus, a laminate in which a copper clad laminate, a photosensitive resin layer, and a support film were laminated in this order was obtained. The obtained laminate was used as a test piece in the test shown below.

(Measurement of light sensitivity)

On the support film of the test piece obtained above, a Hitachi 41-stage stage exposure meter was used, and a direct drawing exposure apparatus (manufactured by Orbotech Ltd., trade name Paragon-9000m, Japan) using a semiconductor laser having a wavelength of 355 nm as a light source was used. Energy exposure.

Next, the support film was peeled off, and a 1.0 mass% sodium carbonate aqueous solution at 30 ° C was sprayed for 45 s to remove the unexposed portion, and development treatment was performed.

After the development treatment, the number of stages of the stage exposure meter of the photocured film formed on the copper clad laminate was measured, and the amount of energy (mJ/cm ² ) in which the number of remaining stages after development was 17.0 was determined. The light sensitivity of the photosensitive resin composition is such that the smaller the energy (mJ/cm ² ), the higher the light sensitivity. The results are shown in Table 5.

(Evaluation of adhesion and resolution)

On the support film of the test piece obtained above, drawing data having a wiring pattern having a line width/void width of 5/5 to 47/47 (unit: μm) as a pattern for evaluation of the resolution was used, and Hitachi 41 was used. The energy of the remaining stage of the stage after the development of the stage exposure table was 17.0 for exposure. After the exposure, the same development processing as the above-described photo sensitivity measurement test was performed.

After the development treatment, the resist pattern was observed using an optical microscope. In the resist pattern in which the void portion (unexposed portion) of the resist pattern is completely removed and the line portion (exposure portion) is not twisted or broken, the resist pattern having the smallest gap width between the line widths is determined as the dense pattern. The properties (μm) and resolution (μm) were evaluated. The smaller the value, the better the adhesion and the resolution. The results are shown in Table 5.

(Evaluation of cover hole reliability)

A copper-clad laminate having a diameter of 1 mm and a circular hole was formed on a 0.4 mm-thick copper clad laminate with a gap of 7 mm, and the photosensitive element obtained above was laminated on both sides thereof, and the Hitachi 41-stage exposure was performed. The amount of energy remaining in the remaining stage of the table after development was exposed to an amount of energy of 17.0. After the exposure, the same developing solution as the light sensitivity measurement test was used, and the development treatment was carried out by spraying for 30 seconds.

After the development, the number of the ruptured photosensitive elements in a total of 320 circular holes was measured, and the cap hole rupture rate was calculated according to the following mathematical formula, and this was taken as the cap hole reliability. The results are shown in Table 5.

Cover hole rupture rate = (hole rupture number / 320) * 100

table 5

As shown in Table 5, the photosensitive elements prepared by the photosensitive resin compositions of Examples 27 to 30 showed significantly higher photosensitivity, cap hole reliability, adhesion, and resolution than Comparative Examples 6-9. For excellent characteristics. In particular, although Comparative Example 7 used a (meth) acrylate compound having a skeleton derived from dipentaerythritol as the component (B), a pyrazoline compound was not used as the component (D) sensitizing dye, and the result was Compared with Examples 27 and 28, it is not only poor in light sensitivity but also poor in cover hole reliability.

As described above, the photosensitive resin composition of Example 27-30 can form a printed wiring board excellent in light sensitivity, lid hole reliability, adhesion, and resolution in an etching process using a direct drawing exposure method.

[Examples 31-35]

Examples 31-35 used D5-D9 as component (D) sensitizing dye, respectively, in place of D1 in Example 27, and other conditions were unchanged. Then, a photosensitive resin composition, a photosensitive element, and a laminate were produced by the method described in Example 27, and evaluated by the same method. The results are shown in Table 6.

Table 6

DD	实施例31Example 31	实施例32Example 32	实施例33Example 33	实施例34Example 34	实施例35Example 35
D5D5	0.250.25
D6D6		0.250.25
D7D7			0.250.25
D8D8				0.250.25
D9D9					0.250.25
光灵敏度(mJ/cm²)Light sensitivity (mJ/cm ² )	3030	3030	3030	3030	3030
密合性(μm)Adhesion (μm)	1515	1414	1515	1313	1212
晰像度(μm)Resolution (μm)	1515	1414	1515	1313	1212
盖孔破裂率(％)Cover hole rupture rate (%)	00	00	00	00	00

The structure of D5-D9 is as follows:

As shown in Table 6, when a sensitizing dye is selected from a pyrazoline (particularly a compound corresponding to the formula (I) or (II)), the photosensitive resin composition also exhibits light sensitivity and lid hole reliability. Excellent adhesion and resolution.

[Examples 36-39]

In Examples 36-39, B1 in Example 28 was replaced by B6-B9, and the other conditions were unchanged. Then, a photosensitive resin composition, a photosensitive element, and a laminate were produced by the method described in Example 28, and the same method was employed. Conduct an evaluation. The results are shown in Table 7.

Table 7

BB	实施例36Example 36	实施例37Example 37	实施例38Example 38	实施例39Example 39
B6B6	1010
B7B7		1010
B8B8			1010
B9B9				1010
光灵敏度(mJ/cm²)Light sensitivity (mJ/cm ² )	3535	3535	5050	5050
密合性(μm)Adhesion (μm)	1515	1414	1515	1111
晰像度(μm)Resolution (μm)	1515	1414	1515	1111
盖孔破裂率(％)Cover hole rupture rate (%)	00	00	00	00

In Table 7, B6: a compound of the formula (1) wherein n = 1, A is an ethyl group, and R ₉ is a methyl group. B7: A compound of the formula (1) wherein n = 5, A is ethyl and R ₉ is methyl. B8: A compound of the formula (1) wherein n = 1, A is a propyl group and R ₉ is a methyl group. B9: A compound of the formula (1) wherein n = 5, A is a propyl group, and R ₉ is a methyl group.

As shown in Table 7, although the (meth) acrylate compound having a skeleton derived from dipentaerythritol was changed, the photosensitive resin composition was the same under the premise of the structural range represented by the general formula (1). It exhibits excellent characteristics of light sensitivity, lid hole reliability, adhesion, and resolution.

From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:

The compound represented by formula (I) or formula (II) has excellent solubility and absorption band between 360 and 400 nm, and is particularly suitable as a sensitizer for use in a photocuring system, especially a system containing a bisimidazole photoinitiator. It has excellent effect on sensitivity improvement, and the film produced has good resolution and adhesion. And because the molecule contains an alkenyl group or a macromolecular compound, it also has a property of being difficult to migrate in use.

Since the compound represented by the formula (I) or the formula (II) is excellent in solubility, when used in combination with a binder polymer, a photopolymerizable compound having at least one ethylenically unsaturated bond, and a photopolymerization initiator, A good dispersing effect can be formed with each component, the action of each component can be fully exerted, the sensitivity of the photosensitive resin composition can be improved, and the resolution and adhesion of the film structure formed from the composition can be improved. The above description is only the preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims

A pyrazoline-based sensitizer having a structure represented by the following formula (I):

Or have the structure shown in the following formula (II):

among them,

R 1 represents a C 1 -C 10 linear or branched alkyl group, a C 4 -C 10 alkylcycloalkyl group or a cycloalkylalkyl group, a phenyl group, a substituted phenyl group, a C 2 -C 10 alkene group. R 2 represents hydrogen, a C 1 -C 10 linear or branched alkyl group, a C 4 -C 10 alkylcycloalkyl group or a cycloalkylalkyl group; R 3 represents an empty or -CH 2 -CH ( OH)-CH 2 -O-; R 4 represents hydrogen, C 1 -C 10 linear or branched alkyl, C 4 -C 10 alkylcycloalkyl or cycloalkylalkyl; R 5 represents a pyrazole ring having a substituent group of a conjugated structure; R 6 represents hydrogen, a C 1 -C 10 linear or branched alkyl group, a C 4 -C 10 alkylcycloalkyl group or a cycloalkylalkyl group; each independently represent a -O- (CHR 8) m - of repeating units, R 8 are each independently selected from hydrogen, methyl or ethyl, m is an integer of 1 to 6; R 7 has n of external linkages a linear or branched alkyl group selected from C 1 -C 60 , optionally wherein carbon or hydrogen may be substituted by oxygen, sulfur or phenyl; n represents an integer from 1 to 20.
The sensitizer according to claim 1, wherein R 1 is selected from the group consisting of phenyl, substituted phenyl or C 3 -C 6 alkenyl.
The sensitizer according to claim 1 or 2, wherein R 1 is selected from the group consisting of:

C 6 H 5 *, CH 3 C 6 H 4 *, CH 3 CH 2 C 6 H 4 *, CH 3 CH 2 CH 2 C 6 H 4 *, CH 3 CH 2 CH 2 CH 2 C 6 H 4 *, C 6 H 5 C 6 H 4 *, C 6 H 5 C 6 H 4 *, CH 3 CH=CH 2 *, CH 3 CH 2 CH=CH 2 *, CH 3 CH 2 CH 2 CH=CH 2 *, (CH 3 ) 2 CH 2 CH=CH 2 *, CH 3 CH 2 CH 2 CH 2 CH=CH 2 *, C 6 H 5 CH=CH 2 *.
The sensitizer according to claim 1, wherein R 2 is hydrogen or a C 1 - C 4 linear or branched alkyl group.
The sensitizer according to claim 1, wherein R 4 is hydrogen or a C 1 - C 4 linear or branched alkyl group.
The sensitizer according to claim 1, wherein R 5 is selected from the group consisting of phenyl, pyrrolyl, imidazolyl, oxazolyl, fluorenyl or alkenyl, optionally, hydrogen in these groups The atoms may each be independently substituted with a C 1 -C 10 linear or branched alkyl group, a C 4 -C 10 alkylcycloalkyl or cycloalkylalkyl group, a phenyl group, a heteroaryl group.
The sensitizer according to claim 1 or 6, wherein R 5 is selected from the group consisting of:

*CH=CHCH 3 , *CH=CH-CH 2 CH 3 , *CH=CH-CH 2 CH 2 CH 3 , *CH=CH-CH(CH 3 ) 2 , *CH=CH-C 6 H 5 .
The sensitizer according to claim 1, wherein R 6 is selected from the group consisting of hydrogen and a C 1 -C 6 linear or branched alkyl group.
The sensitizer according to claim 1 or 8, wherein R 6 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, CH 3 C (CH 2 CH) 3 ) 2 -.
The sensitizer according to claim 1, wherein A is selected from the group consisting of -[O-(CHR 8 ) m ] y - wherein R 8 is each independently selected from hydrogen or methyl, and m is from 1 to 3. An integer, y stands for 1-9.
The sensitizer according to claim 1 or 10, wherein A is selected from the group consisting of -[OCH 2 ] y -, -[OCH 2 CH 2 ] y -, -[OCH 2 CH 2 CH 2 And y -, -[O-CH(CH 3 )-CH 2 ] y -, -[O-CH 2 -CH(CH 3 )-CH 2 ] y -, wherein y represents an integer of 1-9.
The sensitizer according to claim 1, wherein R 7 is preferably selected from the group consisting of:
The sensitizer according to claim 1, wherein n is an integer of from 1 to 8.
A method for preparing a sensitizer, comprising the steps of:

(1) The raw material a and the raw material b are reacted in a solvent containing a catalyst to form an intermediate a;

(2) intermediate a and raw material c reacted under strong base to form intermediate b;

(3) The intermediate b is deprotected by the action of an acid to obtain an intermediate c;

(4) intermediate c and starting material d in glacial acetic acid at 30-100 ° C for 2-20h to form intermediate d;

When the sensitizer has the formula (I)
Time,

(5) when R 3 is empty: intermediate d and starting material e are reacted in a solvent containing an acid binding agent to form a product;

When R 3 is -CH 2 -CH(OH)-CH 2 -O-: the intermediate d is reacted with epichlorohydrin in a solvent containing a phase transfer catalyst, and after the reaction is completed, a strong base is added to continue the reaction, and the intermediate is obtained. Body e; then reacting intermediate e with starting material f in the presence of a catalyst and a polymerization inhibitor to provide a product;

When the sensitizer has the formula (II)
Time,

(5) Intermediate d is reacted with methyl chloroacetate under the action of an acid binding agent and a catalyst to obtain an intermediate f;

(6) intermediate f and the starting material h undergo a transesterification reaction under the action of a catalyst and a polymerization inhibitor to obtain a product;

The reaction process is as follows:

Wherein R 1 represents a C 1 -C 10 linear or branched alkyl group, a C 4 -C 10 alkylcycloalkyl group or a cycloalkylalkyl group, a phenyl group, a substituted phenyl group, a C 2 -C 10 group ; Alkenyl; R 2 represents hydrogen, C 1 -C 10 linear or branched alkyl, C 4 -C 10 alkylcycloalkyl or cycloalkylalkyl; R 3 represents vacancy or -CH 2 - CH(OH)-CH 2 -O-; R 4 represents hydrogen, C 1 -C 10 linear or branched alkyl, C 4 -C 10 alkylcycloalkyl or cycloalkylalkyl; R 5 a substituent group having a conjugated structure with a pyrazole ring; R 6 represents hydrogen, a C 1 -C 10 linear or branched alkyl group, a C 4 -C 10 alkylcycloalkyl group or a cycloalkylalkyl group; ; a each independently represent a -O- (CHR 8) m - of repeating units, R 8 are each independently selected from hydrogen, methyl or ethyl, m is an integer of 1 to 6; R 7 has n Foreign A linkage, selected from a linear or branched alkyl group of C 1 -C 60 , optionally wherein the carbon or hydrogen may be replaced by oxygen, sulfur or a phenyl group; n represents an integer from 1 to 20.
The process according to claim 14, wherein in the step (1), the catalyst is selected from the group consisting of methanesulfonic acid, p-toluenesulfonic acid and p-toluenesulfonic acid pyridinium.
The preparation method according to claim 14, wherein in the step (2), the strong base is potassium hydroxide, sodium hydroxide or barium hydroxide.
The process according to claim 14, wherein the deprotection in the step (3) is carried out by dissolving the intermediate b in a hydrocarbon solvent containing an acid for hydrolysis.
The preparation method according to claim 14, wherein when the sensitizer has the formula (I), in the step (5), when R 3 is empty, the acid binding agent is selected from the group consisting of three Amine, potassium carbonate, ethylenediamine, pyridine, the solvent is selected from the group consisting of benzene, toluene, dichloromethane, and dichloroethane.
The preparation method according to claim 14, wherein when said sensitizer has formula (I), in step (5), when R 3 is -CH 2 -CH(OH)-CH 2 -O When the phase transfer catalyst is selected from a quaternary ammonium salt catalyst such as tetramethylammonium bromide, tetrabutylammonium bromide or tetrapropylammonium bromide or a basic catalyst such as dimethylimidazole, The strong base is sodium hydroxide and/or potassium hydroxide, the catalyst is triphenylphosphine, and the polymerization inhibitor is p-hydroxyanisole.
The preparation method according to claim 14, wherein when the sensitizer has the formula (II), the acid binding agent in the step (5) is pyridine, triethylamine or potassium carbonate. The catalyst is potassium iodide or sodium bromide.
The preparation method according to claim 14, wherein when the sensitizer has the formula (II), in the step (6), the catalyst is a titanate compound.
The preparation method according to claim 20, wherein the titanate compound is 2-ethylhexyl titanate, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate. One or a combination of two or more of tetraisobutyl titanate and tetrakis(2-ethylhexyl) titanate.
The preparation method according to claim 21, wherein in the step (6), the polymerization inhibitor is selected from the group consisting of p-hydroxyanisole, N, N-diethylhydroxylamine, hydroquinone, ortho-benzene. Diphenol, p-tert-butyl catechol, methylhydroquinone, p-methoxyphenol, phenothiazine, triphenylphosphine.
Use of the sensitizer of any of claims 1-13 in a photocurable composition.
The use according to claim 23, wherein the photocurable composition contains a bisimidazole photoinitiator.
A photosensitive resin composition comprising the following components: (A) a binder polymer; (B) a photopolymerizable compound having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) The sensitizing dye, the sensitizing dye as the component (D) contains a pyrazoline compound, and the pyrazoline compound is the sensitizer according to any one of claims 1 to 13.
The photosensitive resin composition according to claim 25, wherein the binder polymer as the component (A) is selected from the group consisting of an acrylic resin, a styrene resin, an epoxy resin, an amide resin, and an amide. One or more of an epoxy resin, an alkyd resin, and a phenol resin.
The photosensitive resin composition according to claim 25, wherein the (A) binder polymer has a structural unit content of a polymerizable monomer having a carboxyl group of 12 to 50% by mass.
The photosensitive resin composition according to claim 25, wherein the component (B) comprises a (meth) acrylate compound having a skeleton derived from dipentaerythritol.
The photosensitive resin composition according to claim 28, wherein the (meth) acrylate compound having a skeleton derived from dipentaerythritol has a structure represented by the formula (1):

In the formula (1), R 9 each independently represents a hydrogen atom or a methyl group, and A each independently represents a C 2 -C 6 alkylene group, and n is an integer of 0-20.
The use of the photosensitive resin composition according to any one of claims 25 to 29 for producing a photosensitive element and a laminate, producing a resist pattern, and producing a printed wiring board and a lead frame.