KR20170141708A - Pyrazoline-based sensitizer, its preparation method and its application - Google Patents

Abstract

A pyrazoline-based sensitizer, and a production method and application thereof are disclosed. The pyrazoline sensitizer has the structure shown in formula (I) or (II), the absorption band is between 350-440 nm, and is used in a system containing a photocuring system, in particular a diimidazole photoinitiator And the formula (I) and the formula (II) are as follows.

Description

Pyrazoline-based sensitizer, its preparation method and its application

The present invention belongs to the field of organic chemistry and specifically relates to a pyrazoline type sensitizer, a method for producing the sensitizer, a use of the sensitizer in the field of photocuring, a photosensitive resin composition, a photosensitive resin laminate comprising the photosensitive resin composition, A method of forming a resist pattern on a substrate using the photosensitive resin laminate, and a use of the resist pattern.

Ultraviolet light curing technology has been widely applied because of its advantages such as quick curing speed and low environmental pollution. The photoinitiator therein plays a crucial role in the curing efficiency of the overall curing system. In practical use, some photoinitiators can not initiate polymerization smoothly due to limited wavelength absorption, and therefore, a sensitizer should often be used together to increase the initiation efficiency. The sensitizer can continuously transfer the energy it absorbs to the photoinitiator and corresponds to the catalyst of the photochemical reaction. However, the application of sensitizers is limited by several factors such as solubility and matching of absorption wavelength. At this stage, the search for a sensitizer having an excellent affinity by matching with the absorption wavelength of the photoinitiator has been a subject of intense research in the above-mentioned field.

Pyrazoline compounds are already known as sensitizers. For example, Chinese patent applications CN101652715A and CN102375341A disclose application of different pyrazoline compounds to photosensitive resins. However, these conventional pyrazoline-based compounds have some disadvantages such as poor solubility when used as a sensitizer and poor sensitivity-improving effect.

Currently, printed circuit boards are manufactured through photolithography. The photolithography method is a method in which a photosensitive resin composition is applied to a substrate and subjected to pattern exposure to polymerize and cure an exposed portion of the photosensitive resin composition and then a portion unexposed by the developer is removed to form a resist pattern on the substrate, After the conductor pattern is formed by the treatment, the resist pattern is removed from the substrate to form a conductor pattern on the substrate.

In the photolithography method, when a photosensitive resin composition is applied to a substrate, a method of applying a photosensitive resin composition solution (that is, a photoresist solution) to the substrate and drying the substrate is used, or a method of forming a layer comprising a support and a photosensitive resin composition (Hereinafter referred to as a " photosensitive resist dry film "or a" dry film resist ") composed of a photosensitive resin layer (hereinafter referred to as a " photosensitive resin layer " In the manufacture of printed circuit boards most of the latter photosensitive resist dry films are used.

Hereinafter, a method of manufacturing a printed circuit board using the dry film resist will be briefly described. First, if a protective layer such as a polyethylene thin film is provided, it is peeled from the photosensitive resin layer. Then, the photosensitive resin layer and the support are laminated on the substrate such as a copper clad laminate in the order of the substrate, the photosensitive resin layer, and the support using a laminating apparatus. Thereafter, the photosensitive resin layer was exposed to ultraviolet light such as i-line (365 nm) emitted by a high-pressure mercury lamp through a photomask provided with a wiring pattern to polymerize and cure the exposed portion, and then the support formed of polyethylene terephthalate was peeled off . Subsequently, the unexposed portions of the photosensitive resin layer are dissolved or dispersedly removed through a developer such as an aqueous alkaline solution to form a resist pattern on the substrate. Thereafter, using the formed resist pattern as a protection mask, a known etching treatment or pattern plating treatment is performed. Finally, the resist pattern is peeled off the substrate to form a substrate having a conductor pattern, that is, a printed circuit board.

In the case of using a dry film resist, in the developing step of dissolving the unexposed portion into a weakly alkaline aqueous solution, the unpolymerized composition is dispersed in the developing solution. When such a dispersion is agglomerated, agglomerates are formed in the developer. In the case where agglomerates are generated much, there is a problem that the frequency of replacing the filter is increased in the process of circulating the developer through the filter, or the cleaning cycle of the developing device is shortened . Therefore, some measures have been taken to alleviate this problem. For example, hydrophilicity of a hydrophilic group formed by adding an ethylene oxide chain or the like to a monomer or a polymer increases the hydrophilicity of the aggregate; Attempts have been made to reduce the aggregates using nonylphenol-type monomers. However, these attempts can not completely solve the problem. Therefore, it is expected that a novel photosensitive resin composition capable of suppressing the occurrence of agglomerates of the developer is expected to be developed.

On the other hand, as the printed circuit board has recently become finer and the market scale has been enlarged, a higher requirement has been raised for the sensitivity (for shortening the exposure time) and the resolution of the photosensitive resin composition, starting from the viewpoints of production efficiency and product quality .

For example, low-molecular weight sensitizers have been basically discontinued due to problems such as odor and toxicity, and most of the currently used sensitizers are limited in their use due to their solubility and absorption wavelength limitations, The present invention provides a pyrazoline-based sensitizer, a method for producing the same, and an application thereof.

A first aspect of the present invention provides an alkenyl-containing pyrazoline sensitizer. When applied to a photocurable system, the sensitizer is extremely ideal in solubility, has no odor, and has excellent sensitivity improving effect, and the produced film has excellent resolution and adhesion. In addition, since it contains an alkenyl group in the molecule, it further has a feature that it is not easily transited during use.

The alkenyl-containing pyrazoline sensitizer of the present invention has the structure shown in the following formula (I)

Wherein R ₁ represents C ₁ -C ₁₀ straight or branched chain alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl, phenyl, substituted phenyl or C ₂ -C ₁₀ alkenyl; R ₂ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl; R ₃ represents a direct bond (empty) or -CH ₂ -CH (OH) -CH ₂ -O-, and a direct bond (vacant) represented by R ₃ represents a direct bond between O and a benzene ring ; R ₄ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl. As a preferred technique, R ₁ in formula (I) is selected from phenyl, substituted phenyl or C ₃ -C ₆ alkenyl; More preferably, R ₁ is 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) is selected from _{2 CH 2 CH = CH2 *,} CH 3 CH 2 CH 2 CH 2 CH = CH group in the _{2 *, C 6 H 5 CH} = CH 2 *. R ₂ is preferably hydrogen, C ₁ -C ₁₀ straight or branched chain alkyl, more preferably hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl. R ₄ is preferably hydrogen, C ₁ -C ₁₀ linear or branched alkyl, more preferably hydrogen, methyl, ethyl, propyl or isopropyl.

By making the above-mentioned selection on the above-mentioned groups, on the one hand, it is easy to synthesize the target substance on the basis of being capable of ensuring the realization of the technical effect of the present application; On the other hand, since it is easy to obtain a corresponding synthetic raw material, the manufacturing cost is relatively low.

Another object of the present invention is to provide a process for producing an alkenyl-containing pyrazoline sensitizer having the structure of the formula (I)

(1) reacting the raw material a and the raw material b in a solvent containing a catalyst to produce an intermediate a; (2) a step in which intermediate a and raw material c react under the action of strong alkali to produce intermediate b; (3) deprotecting intermediate b under the action of an acid to obtain intermediate c; (4) Intermediate c and raw material d are reacted in glacial acetic acid at 30-100 캜 for 2-20 h to produce intermediate d; (5) When R ₃ is a direct bond (empty), the intermediate d and the raw material e react in a solvent containing an acid-binding agent to produce a product; When R ₃ is -CH ₂ -CH (OH) -CH ₂ -O-, intermediate d and epichlorohydrin are reacted in a solvent containing a phase transfer catalyst, and after completion of the reaction, To continue the reaction to obtain an intermediate e; And then reacting the intermediate e and the starting material f with a catalyst in the presence of a polymerization inhibitor to obtain a product; The reaction and formula are as follows.

Raw material a  Raw material b Intermediate a Raw material c Intermediate b

 Intermediate c     Raw material d Intermediate d

Raw material e product

Intermediate e Raw material f product

The sensitizer of the present invention is based on improvement and optimization of the compound structure. As shown in the above reaction formula, for example, reference may be made to the contents described in International Patent Nos. WO2009 / 060235A and CN1515557A, and the full text thereof is incorporated herein by reference.

Specifically, in step (1), the solvent to be used is not particularly limited and may be any conventional organic solvent which can dissolve the reaction raw material but does not participate in the reaction, for example, dichloromethane, dichloroethane, toluene, , Xylene, and the like may be used. The catalyst may be selected from methyl sulfonic acid, para toluene sulfonic acid, pyridinium para-toluene sulfonate.

In step (2), the strong alkali is potassium hydroxide, sodium hydroxide or barium hydroxide. The reaction proceeds in an organic solvent, and there is no particular limitation on the type of solvent, and generally alcohol solvents such as methanol and ethanol are used. The reaction temperature and the reaction time differ depending on the structure of the raw material c. Usually, the reaction temperature is between 0-50 ° C, and the reaction time is 1-10h.

The deprotection in step (3) can be carried out by dissolving intermediate b in a hydrocarbon solvent such as dichloromethane, dichloroethane and the like, which contains an acid, as a hydrolysis reaction process. The acid may be concentrated hydrochloric acid, acetic acid, methanesulfonic acid, and the like.

In step (5), when R ₃ is a direct bond, the acid binding agent is selected from triethylamine, potassium carbonate, ethylenediamine, pyridine and the like, and the solvent is selected from the group consisting of benzene, toluene, dichloromethane and dichloroethane And the reaction temperature is -10 to 30 ° C.

When R ₃ is -CH ₂ -CH (OH) -CH ₂ -O-, the reaction of intermediate d with epichlorohydrin may proceed in a hydrocarbon solvent such as benzene, toluene, dichloroethane, etc., A quaternary ammonium salt catalyst such as tetramethylammonium bromide, tetrabutylammonium bromide or tetrapropylammonium bromide, or an alkaline catalyst such as dimethylimidazole, and the reaction temperature is usually 10-150 ° C. After completion of the reaction, the strong alkali 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 parahydroxy anisole, and the reaction temperature is 0-100 ° C.

The compounds of formula (I) of the present invention have no odor, excellent solubility, absorption bands of between 350-450 nm and are used as sensitizers in systems containing photocuring systems, especially diimidazole-based photoinitiators And is excellent in the sensitivity improvement effect, and the produced film has excellent resolution and adhesion. Accordingly, the present invention also relates to the application of the alkenyl-containing pyrazoline sensitizer to the photocurable composition.

With respect to the above-mentioned disadvantages of the prior art, the present invention on the other hand provides a pyrazoline sensitizer. Compared with conventional sensitizers, the sensitizers of the present invention are highly ideal for solubility in photocurable systems and can improve the photosensitivity of photoinitiators very much, and the resulting films have excellent resolution and adhesion.

The pyrazoline sensitizer of the present invention has the structure shown in the following formula (II).

among them,

R ₅ represents a substituent having a conjugated structure with the pyrazole ring; R ₆ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl; A is independently a repeating unit having a structure of -O- (CHR ₈ ) _m -, R ₈ is each independently selected from hydrogen, methyl or ethyl, m is an integer of 1-6; R ₇ has n external linkages and is selected from C ₁ -C ₆₀ straight or branched chain alkyl optionally with carbon or hydrogen thereof substituted by oxygen, sulfur or phenyl; n represents an integer of 1-20.

As a preferred technique, in the structure shown in the above formula (I), R ₅ is selected from phenyl, pyrrolyl, imidazolyl, carbazolyl, indolyl or alkenyl and, optionally, Independently, C ₁ -C ₁₀ straight or branched chain alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl, phenyl, heteroaryl.

Also preferably, R < ₅ > is selected from the following group.

In the structure shown in formula (I), R ₆ is preferably selected from hydrogen, C ₁ -C ₆ linear or branched alkyl, and is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, And more preferably CH ₃ C (CH ₂ CH ₃ ) ₂ -.

In a preferred embodiment, A is selected from - [O- (CHR ₈ ) _m ] _y -, wherein each R ₈ is independently selected from hydrogen or methyl, m is an integer from 1 to 3, 9.

Is, A is also preferably _{- [OCH 2] y -,} - [OCH 2 CH 2] y -, - [OCH 2 CH 2 CH 2] y -, - [OCH (CH 3) -CH 2] _{y -, - [O-CH} 2 -CH (CH 3) -CH 2] y - is selected from the group of, of those, y represents an integer of 1-9.

R ₇ is preferably selected from the following groups:

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

On the other hand, if the above-mentioned selection is made for the above-mentioned group, on the one hand, the implementation of the technical effect of the present application can be ensured, and the synthesis of the target substance is easy; On the other hand, since it is easy to obtain a corresponding synthetic raw material, the manufacturing cost is relatively low.

Accordingly, the present invention also relates to a process for preparing a pyrazoline-based sensitizer having the structure shown in the above formula (II), which comprises the steps of: (1) reacting a raw material a and a raw material b in a solvent containing a catalyst, ≪ / RTI > (2) a step in which intermediate a and raw material c react under the action of strong alkali to produce intermediate b; (3) deprotecting intermediate b under the action of an acid to obtain intermediate c; (4) Intermediate c and raw material d are reacted in glacial acetic acid at 30-100 캜 for 2-20 h to produce intermediate d; (5) reacting intermediate d with methyl chloroacetate under the action of an acid-binding agent and a catalyst to obtain intermediate f; (6) the intermediate f and the starting material h generate an ester exchange reaction under the action of a catalyst and a polymerization inhibitor to obtain a product; The reaction process equation is as follows:

Raw material a    Raw material b  Intermediate a   Raw material c Intermediate b

중간체c 원료d 중간체d 원료g

Intermediate c Material d Intermediate d Material g

Intermediate f Raw material h product

The sensitizer of the present invention is based on improvement and optimization of the compound structure. As shown in the reaction process formula described above, it is also possible to refer to, for example, the contents described in the international patents WO2009 / 060235A and Chinese patent CN1515557A, and the full text is incorporated herein for reference.

Specifically, in step (1), the solvent to be used is not particularly limited and may be any conventional organic solvent which can dissolve the reaction raw material and does not participate in the reaction, for example, dichloromethane, dichloroethane, toluene, An organic solvent such as xylene may be used. The catalyst may be selected from methyl sulfonic acid, para toluene sulfonic acid, pyridinium para-toluene sulfonate.

In step (2), the strong alkali is potassium hydroxide, sodium hydroxide or barium hydroxide. The reaction proceeds in an organic solvent, and there is no particular limitation on the type of the solvent, and generally alcohol solvents such as methanol and ethanol are used. The reaction temperature and the reaction time differ depending on the structure of the raw material c. Usually, the reaction temperature is between 0-50 ° C, and the reaction time is 1-10h.

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

The reaction in step (5) proceeds in a solvent, and the solvent may be any conventional organic reagent which can dissolve the reaction reagent such as acetone, DMF, acetonitrile, etc., but does not participate in the reaction. The acid binder 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 4-18h.

The transesterification reaction in step (6) proceeds in a solvent. Among them, there is no particular limitation on the solvent, and it is preferable that toluene, benzene, xylene and the like are selected as long as each reaction reagent can be dissolved and there is no adverse effect on the reaction. The catalyst is preferably a titanic acid compound, and examples thereof include 2-ethylhexyl titanate, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra (2-ethylhexyl) And one or more of them may be used in combination. The polymerization inhibitor may be at least one selected from the group consisting of hydroxyanisol, N, N-diethylhydroxylamine, hydroquinone, catechol, tert-butylcatechol, methylhydroquinone, p- methoxyphenol, phenothiazine, triphenylphosphine Can be selected. In the transesterification reaction, the molar ratio of the intermediate e to the starting material f is preferably n: 1, the amount of the catalyst to be used is preferably 3 ‰ to 10 ‰ of the total amount of the material, and the amount of the polymerization inhibitor to be used is 3 -10 ‰, the reaction temperature is 70-130 ° C, and the reaction time is 1-8 h.

The compounds shown in the above formula (II) of the present invention are excellent in dissolution performance and have absorption bands of 350-450 nm, and are particularly suitable for use as sensitizers in systems containing photocurable systems, particularly diimidazole-based photoinitiators And excellent in the sensitivity improvement effect, and the produced film has excellent resolution and adhesion. The present invention therefore also relates to the application of said pyrazoline sensitizers in photocurable compositions.

According to another aspect of the present application, there is further provided a photosensitive resin composition comprising: (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 any one of the sensitizers described above. This application discloses that when used in combination with a binder polymer, a photopolymerizable compound having at least one ethylenically unsaturated bond, and a photopolymerization initiator, the compound shown in formula (I) or formula (II) And thus, the action of each component can be sufficiently exhibited, thereby improving the sensitivity of the photosensitive resin composition and improving the resolution and adhesion of the film structure formed from the composition.

The binder polymer as the component (A) is selected from one or more of acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin and phenol resin.

In the binder polymer (A), the content of the structural unit from the polymerizable monomer having a carboxyl group is 12-50 mass%.

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

Further, the (meth) acrylate compound having a skeleton derived from dipentaerythritol has the structure shown in the general formula (1)

일반식 (1)

In general formula (1)

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

The present application further provides application of the photosensitive resin composition to the production of a photosensitive element and a laminate, application of the photosensitive resin composition to a resist pattern, and application of the photosensitive resin composition to a printed circuit board and a lead frame .

The present invention also relates to a photosensitive resin laminate comprising the photosensitive resin composition, a method of forming a resist pattern on a substrate using the photosensitive resin laminate, and a use of the resist pattern. Through the selection of the ingredient combination, the photosensitive resin composition of the present invention can exhibit extremely excellent performance in the application.

The technical solution to which the present invention is applied is that since the formula (I) or the formula (II) introduces an alkenyl group and a polymer group, it excellently dissolves the corresponding compound and has an absorption band between 360-400 nm , Is particularly suitable for use as a sensitizer in systems containing photocurable systems, particularly nonimidazole-based photoinitiators, has excellent photosensitivity enhancement effects, and also has good resolution and adhesion. Further, it is characterized by containing an alkenyl group in the molecule or being a polymer compound, so that it is not easily mobilized during use.

What needs to be explained is that the features of the embodiments and embodiments of the present application can be combined with each other under non-collision situations. Hereinafter, the present invention will be described in detail with reference to examples.

<Photosensitive resin composition>

Hereinafter, each component used in the photosensitive resin composition of the present invention will be described in more detail.

[(A) Binder polymer]

As the component (A) used in the present invention, examples of the binder polymer include an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin and a phenol resin. Starting from the viewpoint of alkali developability, it is preferable to select an acrylic resin. These resins may be used alone or in combination of two or more.

(A) The binder polymer can be produced by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinyltoluene and? -Methylstyrene, polymerizable styrene derivatives substituted at an? -Position or aromatic ring, acrylamide such as diacetone acrylamide, acrylonitrile, (Meth) acrylates such as alkyl (meth) acrylates, benzyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylates, dimethylaminoethyl (meth) acrylates, diethylaminoethyl (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, acrylic monomers such as? -bromoacrylic acid,? -chloroacrylic acid,? -furyl (meth) acrylic acid and? -styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, Eight such as maleic acid monoester, fumaric acid, cinnamic acid, α- cyano-cinnamic acid, itaconic acid, crotonic acid, and can be exemplified by a propynyl olsan. These components may be used alone or in combination of two or more.

As the alkyl (meth) acrylate, for example, compounds represented by the following general formula can be exemplified. The alkyl group in such a compound may be optionally substituted by a group such as a hydroxyl group, an epoxy group, a halogen group and the like.

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 from 1 to 12 carbon atoms.

As the monomer represented by the above general formula, for example, there may be mentioned methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl Dodecyl (meth) acrylate, and benzyl (meth) acrylate. These compounds may be used alone or in combination of two or more.

In addition, from the standpoint of alkali developability, the binder polymer as the component (A) in the present invention preferably contains a carboxyl group, and can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers have. As the above-mentioned polymerizable monomer having a carboxyl group, (meth) acrylic acid and esters thereof are preferable, and methacrylic acid and esters thereof are more preferable.

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

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

In addition, starting from the standpoint of adhesion and chemical resistance, the binder polymer as component (A) in the present invention preferably contains styrene or a styrene derivative as a polymerizable monomer. When the styrene or styrene derivative is used as a copolymerization component, the content (ratio of styrene or styrene derivative to the total polymerizable monomer used) is preferably 10-60 mass% %, More preferably from 15 to 50 mass%. If the content is 10% by mass or more, the adhesion tends to be improved. When the content is 60% by mass or less, that is, a phenomenon that a long time is taken for peeling due to a large glass bottle separation part can be suppressed.

In addition, the content of the structural unit from the styrene or the styrene-based derivative in the binder polymer (A) is related to the above ratio of the styrene or styrene derivative, preferably 10-60 mass%, more preferably 15-50 mass% Is more preferable.

These binder polymers may be used alone or in combination of two or more. As the binder polymer when used in combination of two or more kinds, for example, two or more kinds of binder polymers composed of different copolymerization components and two or more kinds of binder polymers having different degrees of dispersion can be exemplified.

The binder polymer (A) may be prepared by a conventional method. Specifically, it can be produced, for example, by radical polymerization of alkyl (meth) acrylate and (meth) acrylic acid, styrene and the like.

Starting from a balance of mechanical strength and alkali developability, the weight average molecular weight of the binder polymer (A) is preferably 20,000 to 300,000, more preferably 40,000 to 150,000, and even more preferably 40,000 to 150,000 , Particularly preferably 50000-80000. The weight average molecular weight in the present invention is a value obtained by converting the weight average molecular weight through a gel permeation chromatography method into a calibration curve prepared using standard polystyrene.

With respect to the content of the binder polymer (A), the amount of the components (A) and (B) relative to 100 parts by mass of the total amount is preferably 30-80 parts by mass, more preferably 40-75 parts by mass, It is more desirable to be negative. When the content of the component (A) is within the above range, the film coating property of the photosensitive resin composition and the strength of the photocurable product are better.

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

Starting from the standpoint of clarity and tenting reliability, the component (B) used in the present invention is a photopolymerizable compound having at least one ethylenically unsaturated bond, and is a (meth) acrylate having at least a skeleton derived from dipentaerythritol Lt; / RTI &gt; compound. Here, the meaning of the (meth) acrylate having a skeleton derived from dipentaerythritol is defined as an esterified product of dipentaerythritol and (meth) acrylic acid and a compound obtained by subjecting the ester compound to an alkylene group modification. The number of ester bonds in a single molecule is preferably 6, and compounds having an ester bond number of 1-5 may be mixed.

As the (meth) acrylate having a skeleton derived from dipentaerythritol, more specifically, for example, compounds represented by the following general formula (1) can be exemplified.

일반식 (1)

In general formula (1)

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

From the viewpoint of sensitivity, adhesion and resolution, it is preferable that R ₉ in the general formula (1) is a methyl group. n is preferably 0 to 15, more preferably 0 to 10, and still more preferably 0 to 5.

In addition, starting from the viewpoint of balance of tenting reliability and resolution, the content of the (meth) acrylate compound having a skeleton derived from the dipentaerythritol with respect to the components (A) and (B) in a total amount of 100 parts by mass Is preferably 3-25 parts by mass, more preferably 5-20 parts by mass.

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

Examples of other photopolymerizable compounds include compounds obtained by reacting an?,? - unsaturated carboxylic acid with a polyol, urethane monomers such as a bisphenol A (meth) acrylate compound and a (meth) acrylate compound having a urethane bond, (Meth) acrylate, nonylphenoxy octaethyleneoxy (meth) acrylate,? -Chloro-? -Hydroxypropyl-? '- (meth) acrylamide ethyl- phthalate,? -Hydroxyethyl ? '- (meth) acryloyloxyethyl-phthalate,? -hydroxypropyl-?' - (methyl) acryloyloxyethyl-phthalate and methacrylate. These compounds may be used alone or in combination of two or more.

Among these compounds, it is preferable to start with a viewpoint of improving tent reliability and resolution in a balanced manner and to contain a bisphenol A (meth) acrylate compound. As the bisphenol A-based (meth) acrylate compound, 2,2-bis (4 - ((meth) acryloyloxypolybutoxy) Bis (4 - ((meth) acryloyloxypolybutoxy) phenyl) propane, 2,2-bis Polyethoxypolypropoxy) phenyl) propane, and the like. These compounds may be used alone or in combination of two or more.

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

Examples of the compound obtained by reacting the above-mentioned?,? - unsaturated carboxylic acid with a polyol include polyethyleneglycol di (meth) acrylate having 2-14 ethylene groups and polypropyleneglycol di (Meth) acrylate, polyethylene glycol polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane polyethylene tri (meth) acrylate having the number of ethylene groups of 1-21 Tetramethylolmethane polyethylene terephthalate (meth) acrylate having a number of ethylene groups of 1-21, and tetramethylolmethane polyethylene terephthalate (meth) acrylate having a number of ethylene groups of 1-30. These compounds may be used alone or in combination of two or more.

Among the above contents, it is preferable to start from the viewpoint of improving tent reliability and resolution, and to contain trimethylolpropane polyethylene tri (meth) acrylate having the number of ethylene groups of 1-21.

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

As the urethane monomer, for example, a (meth) acrylic acid monomer having a hydroxy group at the? -Position is reacted with isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate and 1,6-hexamethylene (Meth) acryloyloxy tetraethylene glycol isocyanate) hexamethylene isocyanate, EO-modified urethane di (meth) acrylate, and EO, PO-modified urethane di (meth) acrylate are used as the diisocyanate compound. Among them, EO represents ethylene oxide, EO-modified compound has a block structure of ethylene oxide group, PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide group Respectively.

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

These other photopolymerizable compounds may be used alone or in combination of two or more.

The content of the component (B) is preferably 20-70 parts by mass, more preferably 25-60 parts by mass, and most preferably 30-60 parts by mass based on 100 parts by mass of the components (A) and (B) More preferably 50 parts by mass. When the content of the component (B) is in the above range, the photosensitivity of the photosensitive resin composition and the film coating property become better.

[(C) Photopolymerization initiator]

The photopolymerization initiator as the component (C) is at least one selected from the group consisting of benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ] -2-morpholino-propanone-1-one aromatic ketones, quinones such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyl dimethyl ketal , 2- (o-chlorophenyl) -4,5-diphenyl-imidazole dimer and 2- (o-fluorophenyl) -4,5-diphenyl imidazole dimer. Acridine derivatives such as ditol dimer, 9-phenylacridine, and 1,7- (9,9'-acridinyl) heptane can be exemplified. These compounds may be used alone or in combination of two or more.

The initiator preferably contains 2,4,5-triarylimidazole dimer. As the 2,4,5-triarylimidazole dimer, for example, 2- (o-chlorophenyl) -4,5-bis- (m-methoxyphenyl) imidazole dimer, 2,2 ', 5- Dimethoxyphenyl) -4 ', 5'-diphenyl-1,1'-imidazole dimer, 2,2', 5-tri (2- Dimethoxyphenyl) -4 ', 5'-diphenyl-1,1'-imidazole dimer, 2,2'-di (2,4-dichlorophenyl) - 4- (2-chlorophenyl) -5- (3, 4-difluorophenyl) 4-dimethoxyphenyl) -4 ', 5'-diphenyl-1,1'-imidazole dimer, and the like.

The content of the component (C) may be from 0.01 to 30 parts by mass, preferably from 0.1 to 10 parts by mass, more preferably from 1 to 7 parts by mass, relative to the components (A) and (B) More preferably 2-6 parts by mass, and particularly preferably 3-5 parts by mass. When the content is 0.1 part by mass or more, the photosensitivity, resolution or adhesion tends to be improved, and when it is 10 parts by mass or less, the resist shape tends to be excellent.

[(D) Increasing dye]

The sensitizing dye as the component (D) contains a pyrazoline compound. (Meth) acrylate compound having a skeleton derived from dipentaerythritol as a photopolymerizable compound, it is possible to provide a photosensitive resin composition which is excellent in photosensitivity and which has excellent tenting reliability, adhesion, and resolution of the formed resist film, A composition can be obtained.

The pyrazoline compounds used as the sensitizing dyes can be exemplified by, for example, compounds having the structures represented by the formulas (I) and (II)

In formula (I)

R ₁ represents C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl, phenyl, substituted phenyl, C ₂ -C ₁₀ alkenyl; R ₂ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl; R ₃ represents a direct bond (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.

In the formula (II)

R ₅ represents a substituent having a conjugated structure with the pyrazole ring; R ₆ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl; A is independently a repeating unit having an -O- (CHR ₈ ) _m- structure, R ₈ is each independently selected from hydrogen, methyl or ethyl, m is an integer from 1 to 6; R ₇ has n external linkages and is selected from C ₁ -C ₆₀ straight or branched chain alkyl optionally with carbon or hydrogen thereof substituted by oxygen, sulfur or phenyl; n represents an integer of 1-20.

More information on the compounds shown in the above Formulas (I) and (II) can be found in the Chinese patent application filed with application numbers 201510264670.9 and 201510263189.8, respectively, .

The content of the compounds represented by the formulas (I) and (II) in the sensitizing dyes of the component (D) is preferably 10-100% by mass, more preferably 30-100% by mass, Particularly preferably in mass%. When the content is 10% by mass or more, it is easy to increase the sensitivity and the resolution.

(D) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and most preferably 0.1 to 3 parts by mass with respect to the components (A) and (B) in a total amount of 100 parts by mass, It is more preferable to set it to the mass part. When the content is 0.01 parts by mass or more, the photosensitivity and resolution tend to be obtained easily. When the content is 10 parts by mass or less, a satisfactory resist shape tends to be easily obtained.

[Other ingredients]

In the photosensitive resin composition of the present invention, a dye such as malachite green, Victoria pure blue, brilliant green and methyl violet, tribromophenylsulfone, colorless crystal violet, diphenylamine, benzylamine, triphenylamine, di A coloring agent such as ethyl aniline, o-chloroaniline, and t-butyl catechol, a plasticizer such as a heat development inhibitor and a p-toluenesulfonamide, a pigment, a filler, a defoaming agent, a flame retardant, an adhesion promoter, a leveling agent, , A perfume, a developer, a heat crosslinking agent, a polymerization inhibitor, and the like. These components may be used alone or in combination of two or more. May be 0.01-20 parts by mass per 100 parts by mass of the components (A) and (B), for each of the additional auxiliaries.

The photosensitive resin composition of the present invention may contain at least one organic solvent as required. As the organic solvent, a commonly used organic solvent can be used, and there is no particular limitation. Specifically, solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether and the like or mixed solvents of these can be listed .

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

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

As the metal plate, for example, an iron alloy such as copper, a copper alloy, nickel, chromium, iron, and stainless steel can be exemplified, and copper, a copper alloy, and an iron alloy are preferable.

The thickness of the photosensitive resin layer to be formed varies depending on the application, but is preferably about 1 to 100 mu m in terms of the thickness after drying. The protective film can cover the surface of the photosensitive resin layer, that is, the surface opposite to the surface on which the support is formed. The protective film may be a polymer film such as polyethylene or polypropylene.

<Photosensitive element>

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

[Support]

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

The thickness of the support (hereinafter also referred to as "support film") is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and even more preferably 1 μm to 30 μm. When the thickness of the support is 1 mu m or more, rupture of the support film can be suppressed when the support film is peeled off. In addition, when the thickness is set to 100 탆 or less, a reduction in resolution can be suppressed.

[Protection film]

If necessary, the photosensitive element may further comprise a protective film covering the other side of the photosensitive resin layer.

As the protective film, it is preferable that the adhesive force to the photosensitive resin layer is smaller than the adhesive force of the supporting film to the photosensitive resin layer, and more preferably, the film has a small fish eye.

Here, the term "fish eye" means that when a film is produced by thermally melting a material constituting the protective film and subjecting the film to blending, extrusion, biaxial stretching, casting or the like, foreign matter, unmelted material, It says. That is, "less fish eyes" means that there are few defects such as foreign matter in the film.

Specifically, as the protective layer, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene and polyester can be used. In addition, the protective film may be the same as the support. The thickness of the protective film is preferably from 1 탆 to 100 탆, more preferably from 5 탆 to 50 탆, even more preferably from 5 탆 to 30 탆, and particularly preferably from 15 탆 to 30 탆. When the thickness of the protective film is 1 占 퐉 or more, the protective film can be peeled off and the protective film can be prevented from rupturing when the photosensitive resin layer and the support film are laminated on the substrate. In addition, if it is set to 100 μm or less, the production rate can be improved.

[Manufacturing method]

The photosensitive element of the present invention can be produced through a manufacturing method including, for example, the following processes. The process comprises the steps of: (A) dissolving components such as a binder polymer, (B) a polymerizable compound, (C) a photopolymerization initiator and (D) a sensitizing dye in an organic solvent to form a coating solution; Coating the coating solution on a support to form a coating layer; And drying the coating layer to form a photosensitive resin layer.

The coating of the coating liquid on the support may be carried out by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater and a spray coater.

The drying of the coating layer only needs to remove at least some organic solvent from the coating layer, and there is no particular limitation. For example, at 70-150 ° C for 5-30 minutes. In order to prevent the organic solvent from diffusing in the subsequent process, it is preferable that the amount of the organic solvent remaining in the photosensitive resin layer after drying is 2% by mass or less.

The thickness of the photosensitive resin layer in the photosensitive element may be appropriately selected depending on the application, and is preferably 1 占 퐉 to 200 占 퐉, more preferably 5 占 퐉 to 100 占 퐉, more preferably 10-50 占 퐉 Particularly preferred. When the thickness is 1 占 퐉 or more, the industrial coating is easy and the production rate is improved. When the thickness is 200 mu m or less, the effects of the present invention can be sufficiently obtained, the photosensitivity can be improved, and the photocurability of the resist bottom tends to be excellent.

If necessary, the photosensitive element of the present invention may further comprise an intermediate layer such as a buffer layer, an adhesive layer, a light absorbing layer, or an air barrier layer.

The form of the photosensitive element of the present invention is not particularly limited. For example, in the form of a piece, or in the form of a roll on the winding core.

When wound in roll form, it is preferable to wind in such a manner that the support film is formed on the outside. As the winding core, for example, a plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin or ABS (acrylonitrile-butadiene-styrene copolymer) can be listed.

It is preferable to start from the standpoint of end face protection and to provide a cross sectional plate at the end face of the roll-shaped photosensitive element roll obtained as described above. From the standpoint of content fusing at the edge, It is desirable to install a plate. In addition, as the packaging method, it is preferable to pack it in a black sheet having low moisture permeability.

The photosensitive element of the present invention can be applied to, for example, a method of manufacturing a resist pattern to be described later.

&Lt; Method of producing resist pattern >

A method for producing a resist pattern of the present invention includes the steps of: (i) forming a photosensitive resin layer from the photosensitive resin composition on a substrate; (ii) an exposure step of irradiating at least a part of the photosensitive resin layer with an actinic ray to photo-cure the exposed part; (iii) removing the uncured portion of the photosensitive resin layer from the substrate via development. If necessary, other processes may be further included.

(i) Photosensitive resin layer forming step

In the step of forming a photosensitive resin layer, a photosensitive resin layer from the photosensitive resin composition is formed on a substrate. The substrate is not particularly limited, and a substrate for circuit formation having a conductor layer formed on an insulating layer and an insulating layer, or a die pad (substrate for a lead frame) such as an alloy substrate may be used.

As a method of forming a photosensitive resin layer on a substrate, for example, when the photosensitive element is provided with a protective film, the protective film is removed, and then the photosensitive resin layer of the photosensitive element is heated, (Not shown). As a result, a laminate composed of a substrate for circuit formation, a photosensitive resin layer, and a support is sequentially obtained.

Starting from the standpoint of adhesion and followability, it is preferable that the step of forming the photosensitive resin layer proceeds under reduced pressure conditions. Heating at the time of pressure welding proceeds at a temperature of 70-130 ° C. In addition, it is preferable that the pressure contact is carried out under a pressure of about 0.1 to 1.0 MPa (about 1-10 kgf / cm ² ). These conditions can be selected as appropriate. In addition, when the photosensitive resin layer is heated to 70 to 130 占 폚, it is not necessary to preheat the substrate for circuit formation in advance, but the substrate for circuit formation may be preheated to further improve the adhesion and followability have.

(ii) exposure step

In the exposure step, at least a part of the photosensitive resin layer formed on the substrate is irradiated with an actinic ray to photo-cure the exposed portion irradiated with the actinic ray to form a latent image.

At this time, in the case where the support (support film) present on the photosensitive resin layer is transparent to the active ray, the support film can be transmitted to irradiate the active ray. When the support film is shielded from light, And irradiates an actinic ray.

As an exposure method, a method of irradiating an active ray in an image shape with a negative or positive mask pattern called a wiring diagram (ART WORK) interposed therebetween can be enumerated (mask exposure method). In addition, a method of irradiating an active ray in an image form through a direct imaging exposure method such as an LDI (Laser Direct Imaging) exposure method, a DLP (Digital Light Processing, Digital Optical Processing) exposure method, or the like may be used.

The light source as the active ray may be a known laser such as a gas laser such as a carbon arc, a mercury vapor arc, an ultra high pressure lamp, a high pressure lamp, a xenon lamp or an argon gas laser, a solid laser such as a YAG laser, And a blue light source such as a violet laser capable of effectively emitting ultraviolet rays. In addition, a light source that can effectively emit visible light such as a photographing Floodlight, daylight, or the like may be used.

In the photosensitive resin composition of the present invention, there is no particular limitation on the kind of the light source of the active ray, and it is preferable to adopt the direct imaging exposure method.

(iii) development process

In the developing step, the uncured portion of the photosensitive resin layer is removed from the substrate through development, and a resist pattern composed of a cured product after the photosensitive resin layer is photo-cured on the substrate is formed.

When the support film is present on the photosensitive resin layer, after removing the support film, the unexposed portions other than the exposed portions are removed (development). The developing method has a wet phenomenon and a dry phenomenon.

In the case of wet developing, the photosensitive resin composition and the corresponding developing solution are used for development through a known developing method. As a developing method, a method such as an immersion method, a stirring method, a spraying method, a scrubbing method, a tapping method, a blade coating, a vibration dipping and the like can be enumerated. Two or more of the above methods may be combined and developed.

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

When an alkaline aqueous solution is used as a developer, it is safe, stable, and operable. The alkali in the alkaline aqueous solution may be, for example, an alkali hydroxide such as a hydroxide of lithium, sodium or potassium, an alkali carbonate such as carbonate or hydrogen carbonate of lithium, sodium, potassium or ammonium, alkali metal phosphate such as alkali phosphate, sodium phosphate, sodium pyrophosphate, Alkali metal pyrophosphate such as potassium phosphate can be used.

0.1-5 mass% sodium carbonate dilute solution, 0.1-5 mass% sodium hydroxide solution, 0.1-5 mass% sodium tetraborate diluted solution, and the like are used as the alkaline aqueous solution used for development. . In addition, the pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature can be adjusted according to the developability of the photosensitive resin layer. In addition, a surfactant, defoaming agent, and a small amount of organic solvent for promoting development can be further mixed in the alkaline aqueous solution.

The aqueous developer is, for example, a developer consisting of water or an alkaline aqueous solution and at least one organic solvent. Here, the alkali of the alkaline aqueous solution may be, for example, borax, sodium silicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3 -Propanediol, 1,3-diamino-2-propanol and morpholine. The pH of the aqueous developing solution is preferably as small as possible within a range in which development can be sufficiently carried out, and it is preferable to set the pH to 8 to 12, more preferably to set to pH 9 to 10.

Examples of the organic solvent used in the aqueous developing solution include 3-acetol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group of 1-4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether and diethylene glycol monobutyl ether. These materials 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 mass%, and the concentration can be adjusted according to developability. A small amount of a surfactant or antifoaming agent may be further mixed in the aqueous developing solution.

As the organic solvent-based developer, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methylisobutylketone and gamma -butyrolactone are listed can do. In order to prevent ignition, it is preferable to add water in the range of 1-20% by mass of the organic solvent.

In the present invention, after removing the unexposed portions in the developing process, the resist pattern may be further cured by heating to about 60 to 250 DEG C or to about 0.2 to 10 J / cm &lt; ² &gt;

<Method of Manufacturing Printed Circuit Board>

The method for manufacturing a printed circuit board of the present invention includes a step of forming a conductor pattern by performing an etching treatment or a plating treatment on a substrate for circuit formation on which a resist pattern is formed. If necessary, it may further include other processes such as a resist removal process. The photosensitive resin composition of the present invention can be applied to the production of a resist pattern, and it is more suitable for a manufacturing method of forming a conductor pattern through plating treatment.

During the etching process, the conductor layer of the substrate for circuit formation, which is not covered with the resist, is removed by etching using the resist pattern formed on the substrate as a mask to form a conductor pattern.

The etching treatment method can be appropriately selected depending on the conductor layer which needs to be removed. For example, the etching solution may be a copper oxide solution, an iron oxide solution, an alkali etching solution, or a hydrogen peroxide etching solution.

On the other hand, in the plating process, using the resist pattern formed on the substrate as a mask, copper plating and solder can be performed on the conductor layer of the substrate for circuit formation which is not covered with the resist. After the plating treatment, the cured resist is removed, and the conductive layer coated with the resist is etched to form a conductor pattern.

As the plating treatment method, it may be an electroplating treatment, an electroless plating treatment, or an electroless plating treatment. As the electroless plating treatment, for example, copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt plating bath (nickel sulfate-nickel chloride plating) and aminosulfamate Nickel plating, gold plating such as nickel plating, hard gold plating, and soft gold plating.

After the etching treatment or the plating treatment, the resist pattern on the substrate is removed. Removal of the resist pattern can be carried out through an aqueous solution having a stronger alkaline property than, for example, the alkaline aqueous solution used in the above-described developing step. As the strongly alkaline aqueous solution, for example, 1-10 mass% sodium hydroxide aqueous solution can be used, and it is preferable to use 1-5 mass% aqueous sodium hydroxide solution.

As the resist pattern peeling method, for example, an immersion method and a spray method can be listed, and this method can be used alone or in combination.

When the resist pattern is removed after the plating process, a desired printed circuit board can be manufactured by etching the conductor layer covered with the resist through the etching process to form a conductor pattern. The etching treatment may be appropriately selected depending on the conductor layer to be removed. For example, the etching solution may be applied.

The printed circuit board manufactured according to the method for manufacturing a printed circuit board of the present invention can be applied not only to the manufacture of a single-layer printed circuit board but also to the manufacture of a multilayer printed circuit board. In addition, through holes, and the like.

<Manufacturing Method of Lead Frame>

The lead frame manufacturing method of the present invention includes a step of forming a conductor pattern by performing a plating process on a substrate on which a resist pattern is formed. And further includes other processes such as a resist removing process and an etching process process, if necessary.

As the substrate, for example, a die pad (substrate for a lead frame) such as an alloy substrate is used as a substrate. In the present invention, a plating process is performed on a substrate using the resist pattern formed on the substrate as a mask.

As the plating treatment method, the methods described in the above-described method for producing a printed circuit board can be enumerated. After the plating process, the resist pattern on the substrate is removed. Removal of the resist pattern can be carried out through an aqueous solution having a stronger alkaline property than, for example, the alkaline aqueous solution used in the above-described developing step. As the strongly alkaline aqueous solution, the aqueous solution described in the above-described method for producing a printed circuit board can be exemplified.

The method of peeling the resist pattern can include an immersion method, a spraying method, and the like, and this method can be used alone or in combination. After the resist pattern is removed, an etching process is further carried out to remove the unnecessary metal layer, whereby the lead frame can be manufactured.

Hereinafter, the beneficial effects of the present invention will be described in more detail by combining Examples and Comparative Examples. The following embodiments are merely illustrative of the embodiments of the present application and are not to be construed as limiting the scope of the claims of the present application.

Example 1

Raw material a   Raw material b Intermediate 1a  Raw material 1c Intermediate 1b

Intermediate 1c Raw material 1d Intermediate 1d

(1) In a 1000 ml four-necked flask, 183 g of parahydroxybenzaldehyde, 5 g of pyridine salt of catalyst p-toluenesulfonic acid and 300 ml of dichloromethane are added, and the temperature is controlled to 50 캜, to which 126 g of dihydropyran is added dropwise. The dropping time is about 1 hour. After the addition is completed, stirring is continued for 10 hours, the liquid phase is traced to stop the reaction if there is no further change in the reaction, and then dichloromethane is removed by rotary evaporation to obtain 275 g of intermediate 1a. The purity is 98% and is used directly in the next step reaction.

(2) 247 g of Intermediate 1a, 144 g of acetophenone and 300 mL of methanol are added to a 1000 mL four-necked flask, stirred with a water bath at room temperature, 80 g of 40% sodium hydroxide solution is added dropwise in 2 h, and stirring is continued for 6 h. The liquid phase was traced to remove any further change in the reaction, followed by filtration, recrystallization from methanol, and drying to obtain 330 g of solid, i.e., Intermediate 1b. The purity is 93%.

(3) 165 g of Intermediate 1b, 30 g of 37% concentrated hydrochloric acid and 500 mL of dichloromethane were added to a 1000 mL four-necked flask, stirred at room temperature for 5 hours, filtered, rinsed with methanol and the solid was dried to obtain 120 g of Intermediate 1c . The purity is 98%.

(4) 112 g of Intermediate 1c and 500 g of glacial acetic acid were added to a 1000 mL four-necked flask, and the temperature was raised to 50 캜 with stirring. Then, 108 g of phenylhydrazine was added dropwise and the dropwise addition was completed for about 2 h. And then recrystallized with methanol to obtain 118 g of intermediate 1d. The purity is 98%.

(5) A mixture of Intermediate 1d (31.4 g, 0.1 mol), triethylamine (12.1 g, 0.12 mol) and dichloromethane (30 mL) was added to a 250 mL four-necked flask and stirred while controlling the temperature in an ice- (9.05 g, 0.1 mol) was added dropwise in the course of stirring, and the reaction was terminated when the reaction was complete. The reaction was stopped by adding 150 ml of water and stirring. The aqueous layer was extracted with dichloromethane, The dichloromethane layer is combined and rotary evaporated to give a white viscous liquid, yielding 36.3 g of product 1. The yield is 99.5% and the HPLC purity is 99%. The reaction formula of step (5) is as follows.

Intermediate 1d Raw material e Product 1

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), 6.40732-6.6221 ), 7.3067-7.6319 (5H, m).

Example 2

Intermediate 1d Intermediate e  Raw material f Product 2

(94.3 g, 0.3 mol), toluene (50 mL), epichlorohydrin (27.8 g, 0.3 mol) and tetrabutylammonium bromide (0.5 g) were charged into a 500 mL four-necked flask, The mixture was allowed to react for 5 h, followed by monitoring the liquid phase until the reaction was completed. Then, the reaction was allowed to proceed to room temperature, 20 g of sodium hydroxide was added, and the temperature was controlled to 30 ° C or lower. After the reaction was completed, 100 mL of water was added to the reaction mixture, the mixture was stirred, toluene was extracted with toluene, the toluene layer was combined, and the mixture was rotary evaporated to obtain 106.6 g of the product intermediate e.

The reaction was carried out at 110 占 폚 for 5 hours by taking 37.0 g of intermediate e, 8.6 g of 0.1 mol of methacrylic acid, 30 mL of toluene, 0.1 g of triphenylphosphine and 0.1 g of parahydroxy anisole. When the reaction is completed, the reaction mixture is cooled to room temperature, the toluene layer is washed with water, the toluene product solution is rotary evaporated, and then recrystallized from methanol to obtain 41.6 g of product 2, with a yield of 88% and a purity of 99% .

The structure of the product 2 is 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 ), 7.0309-7.3067 (7H, m), 7.5927-7.6651 (2H, t).

Examples 3-14

Referring to the method of Example 1 or 2, a product 3-14 having the structure shown below is synthesized.

Product 3 Product 4

Product 5 Product 6

Product 7 Product 8

Product 9 Product 10

Product 11 Product 12

Product 13 Product 14

Example 15

(1) Preparation of intermediate a:

Raw material a   Raw material b Intermediate a

183 g of parahydroxybenzaldehyde, 5 g of the catalyst p-toluenesulfonic acid pyridine salt and 300 ml of dichloromethane are charged into a 1000 ml four-necked flask, and the temperature is controlled at 50 占 폚 to give 126 g of dihydropyran dropwise. The dropping time is about 1 hour. After completion of dropwise addition, stirring is continued for 10 hours, and the liquid phase is traced. When there is no further change in the reaction, the reaction is stopped, and then dichloromethane is removed by rotary evaporation to obtain 275 g of intermediate 1a. The purity is 98% and is used directly in the next step reaction.

(2) Preparation of intermediate 1b:

Intermediate a   Raw material c Intermediate 1b

247 g of Intermediate a, 235 g of 4-phenylacetophenone as raw material c and 300 mL of methanol were charged into a 1000 mL four-necked flask, stirred with a water bath at room temperature, 80 g of a 40% sodium hydroxide solution was added dropwise within 2 h, . If no further changes in the reaction are observed by tracing the liquid phase, the reaction mixture is filtered, recrystallized from methanol and dried to obtain 415 g of a solid, that is, intermediate 1b. The purity is 93%.

(3) Preparation of intermediate 1c:

Intermediate 1b Intermediate 1c

384 g of Intermediate 1b, 50 g of 37% concentrated hydrochloric acid and 500 mL of dichloromethane are added to a 1000 mL four-necked flask, and the mixture is stirred at room temperature for 5 hours, filtered, rinsed with methanol and the solid is dried to obtain 210 g of Intermediate 1c. The purity is 98%.

(4) Preparation of intermediate 1d:

Intermediate 1c Raw material 1d Intermediate 1d

180 g of Intermediate 1c and 500 g of glacial acetic acid were added to a 1000 ml four-necked flask, and the temperature was raised to 50 캜 with stirring. Then, 108 g of phenylhydrazine was added dropwise and the dropwise addition was completed for about 2 h, followed by reaction for 8 h. To obtain 210 g of Intermediate 1d. The purity is 98%.

(5) Preparation of Intermediate 1e:

Intermediate 1d Intermediate 1e

78 g of Intermediate 1d, 3 g of potassium iodide, 35 g of potassium carbonate and 80 mL of acetonitrile are added to a 500 mL four-necked flask, and the mixture is heated to 80 DEG C and refluxed, and then 2 g of methyl chloroacetate is added dropwise. The dropwise completion is completed for about 1 h, and the reaction is continued for 8 h after completion of dropwise addition. After completion of the reaction, when unreacted potassium carbonate is removed by filtration, the precipitated solid is washed with water, extracted, filtered, recrystallized from methanol and dried to obtain 76 g of a light yellow solid, that is, Intermediate 1e. The purity is 99%. The structure of intermediate 1e is confirmed by ¹ H-NMR.

_{^{1 H-NMR (CDCl 3,}} 500MHz): 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 (19 H, m).

(6) Preparation of product 15:

Intermediate 1e Raw material 1f Product 15

74.6 g of the intermediate 1e, 14.3 g of the raw material 1f, 0.1 g of tetraisopropyl titanate, 0.1 g of parahydroxy anisole, and 100 mL of toluene were put into a 500 mL four-necked flask, and the mixture was heated to 90-100 DEG C and stirred. Methanol is evaporated during the heating, and toluene is added in a timely manner. When methanol evaporation disappears, the mixture is filtered while hot. The resulting filtrate is distilled under reduced pressure, and toluene is completely evaporated to obtain 90 g of a pale yellow viscous product .

Example 16

Synthesis of intermediate 2e is carried out with reference to example 15. Preparation of the product 16:

Intermediate 2e Raw material 2f

Product 16

7.36 g of Compound 2e, 27.2 g of the raw material 2f (9-EO), 0.1 g of tetraisopropyl titanate, 0.1 g of parahydroxy anisole and 100 mL of xylene were fed into a 500 mL four-necked flask, The mixture is heated and stirred. Methanol produced by the reaction is evaporated during heating, and when methanol is evaporated in a timely manner, methanol is evaporated. When the evaporation disappears, the reaction product is filtered while hot. The resulting filtrate is distilled under reduced pressure and the toluene is completely evaporated to obtain a pale yellow viscous product, .

Examples 17-26

Referring to the method of Example 15, the product 17-26 having the following structure is synthesized.

Product 17 Product 18

Product 19 Product 20

Product 21 Product 22

Product 23

Product 24

Product 25

Product 26

Performance evaluation

The application performance of the sensitizers shown in the formulas (I) and (II) of the present invention was evaluated through formulation of an illustrative photocurable composition (i.e., photosensitive resin composition).

1. Manufacturing of performance evaluation objects

&Lt; Preparation of photosensitive resin laminate >

The photosensitive resin composition having the components shown in Table 1 and PGMEA (propylene glycol methyl ether acetate) were thoroughly stirred and mixed, and uniformly coated on the surface of a polyethylene terephthalate thin film having a thickness of 19 탆 as a support using a bar coating. Lt; 0 &gt; C for 4 minutes to form a photosensitive resin layer having a thickness of 40 mu m.

Subsequently, a 23 탆 thick polyethylene film as a protective layer was adhered to the surface of the photosensitive resin layer on which the thin film of polyethylene terephthalate was not laminated to obtain a photosensitive resin laminate.

&Lt; Leveling of substrate surface >

As a substrate for evaluation of photosensitivity and resolution, a copper clad laminate treated with a spray cleaning and polishing machine under a spray pressure of 0.20 MPa is prepared.

<Laminating>

The surface is leveled while peeling the polyethylene thin film of the photosensitive resin laminate, and the laminate is preheated to a temperature of 105 DEG C through a hot roll laminator to a temperature of 60 DEG C to laminate the copper clad laminate. The gas pressure was 0.35 MPa and the laminating speed was 1.5 m / min.

<Exposure>

h line type direct-exposure type exposure apparatus, exposure is performed at an exposure amount of 8 in the stepped exposure system according to the following sensitivity evaluation.

<Development>

After the polyethylene terephthalate thin film is peeled off, the unexposed portions of the photosensitive resin layer are removed by spraying with an aqueous solution of sodium carbonate of 1% by mass at 30 占 폚. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion is set as the minimum developing time.

practice
Yes
One Example
2 practice
Yes
3 Example
4 Example
5 practice
Yes
14 Example
15 Example
16 Example
17 Example
18 Comparative Example
One ratio
School
Yes
2 ratio
School
Yes
3 ratio
School
Yes
4 ratio
School
Yes
5





Photosensitive
Number
G
article
castle
water
(Parts by mass)




P-1 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 P-2 10
7 10
7 10
7 10
7 10
7 10
7 10
7 10
7 10
7 10
7 10
7 10
7 10
7 10
7 10
7 M-1 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 M-2 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 M-3 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 M-5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 BCIM 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 product
One

0.3

0.3

0.3 product
2

0.3

0.3 product
3

0.3

0.3 product
6

0.3

0.3 product
12

0.3

0.3 A-1 0.3 A-2 0.3 A-3 0.3 B-1 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.0
4 0.04 0.04 0.04 B-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

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

sign ingredient P-1 Solid component of copolymer 30% by mass of methyl ethyl ketone solution. The copolymer had a composition of methyl methacrylate / methacrylic acid / n-butyl acrylate (weight ratio 65/25/10), an acid equivalent of 344 and a weight average molecular weight of 120000. P-2 Solid component of copolymer 43% by mass of methyl ethyl ketone solution. The copolymer had a composition of methyl methacrylate / methacrylic acid / n-butyl acrylate (weight ratio 50/25/25), an acid equivalent of 340 and a weight average molecular weight of 50,000. M-1 Urethanates of hexamethylene diisocyanate and pentapropylene glycol monomethacrylate M-2 Triethylene glycol dodecyl propylene glycol triethylene glycol,?,? - dimethacrylate M-3 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate M-5 Triacrylate obtained by adding trimethylol propane to an average of 3 moles of cyclohexane BCIM o-chlorohexaryldiimidazole (photoinitiator) A-1 1,5-diphenyl-3-styrene-pyrazoline A-2 4,4'-bis (diethylamino) benzophenone A-3 Phenyl-3- (4-biphenyl) -5- (4-isopropyl-phenyl) -pyrazoline B-1 Malachite Green B-2 Ryuko Crystal Violet

2. Performance evaluation method

(1) Compatibility test

The photosensitive resin composition having the components shown in Table 1 was thoroughly stirred and mixed and uniformly coated on the surface of a polyethylene terephthalate thin film having a thickness of 19 탆 as a support using a bar coating and then dried in a dryer at 95 캜 for 4 minutes Thereby forming a photosensitive resin layer. Thereafter, the coated surface is visually observed and graded according to the following method.

◇ Coating surface is uniform; ◆: Unsoluble material deposited on the coated surface.

(2) Odor evaluation

The photosensitive resin composition thus prepared is evaluated by the Fan Smell method, and classified into the following grades.

○: No odor ◎: With smell

(3) Evaluation of photosensitivity

The substrate after laminating was exposed to light for 15 minutes using a 21 step graded exposure system manufactured by Stouffer having a 21 degree brightness change from transparent to black to evaluate its photosensitivity. After the exposure, the exposure time was twice the development time of the minimum development time, and the grades were classified according to the exposure amount of 8 in the stepwise exposure system in which the resist film completely remained, as follows.

?: Exposure dose less than 20 mJ / cm ² ; ◎: exposure amount is 20mJ / cm ² -50mJ / cm ² Im (not including the final value); ●: Exposure dose is over 50 mJ / cm ² .

(4) Evaluation of resolution

The substrate after the laminating was exposed for 15 minutes through a linear pattern mask having a ratio of the width of the exposed portion and the unexposed portion of 1: 1, and development was then carried out at a developing time twice the minimum developing time, The minimum mask line width forming the line was taken as the resolution value.

?: The resolution value is 30 占 퐉 or less; ⊚: resolution value is 30 탆 -50 탆 (final value not included); ●: Resolution value is over 50㎛.

(5) Evaluation of adhesion

The substrate after the laminating was exposed for 15 minutes through a linear pattern mask having a ratio of the width of the exposed portion and the unexposed portion of 1: 100, and development was then carried out at a developing time twice the minimum developing time, The minimum mask line width forming the line is taken as the adhesion force value.

?: Adhesion value is 30 占 퐉 or less; &Amp; cir &amp;: adhesion value is 30 mu m-50 mu m (final value not included); ●: Adhesion value is over 50㎛.

3. Performance evaluation results

Refer to Table 3 for performance evaluation results.

Example
One Example
2 Example
3 Example
4 Example
5 Example
14 Example
15 Example
16 Example
17 Example
18 compare
Yes
One compare
Yes
2 compare
Yes
3 compare
Yes
4 compare
Yes
5 Prize
for
castle
Rating ◇ ◇ ◇ ◇ ◇
◇
◇
◇
◇
◇
◆ ◇ ◇ ◇ ◇ smell Rating ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ Photosensitive
Degree (mJ / cm &lt; ² &gt; / grade)
15 / ○
15 / ○
15 / ○
10 / ○
10 / ○
20 / ○
15 / ○
20 / ○
20 / ○
15 / ○
*
One
80 / ●
30 / ◎
*
2
*
2 sea
Degree (탆 / grade)
30 / ○
25 / O
30 / ○
25 / O
20 / ○
30 / ○
25 / O
30 / ○
30 / ○
25 / O
*
One
100 / ●
40 / ◎
*
2
*
2 Attach
Power (탆 / grade)
30 / ○
25 / O
30 / ○
25 / O
20 / ○
30 / ○
25 / O
30 / ○
30 / ○
25 / O
*
One
100 / ●
45 / ◎
*
2
*
2

Note: * 1 indicates that dissolution occurred on the surface of the resist and evaluation was impossible.

* 2 is a case where the resist can not be sufficiently cured to form a resist line.

From the evaluation results of Table 3, it can be seen that the composition (Examples 1-5, 14-18) of the present invention using the sensitizer of the present invention has very good compatibility, has no odor, has high photosensitivity Excellent resolution and adhesion were exhibited, which is clearly superior to Comparative Example 1-3 using a conventional sensitizer. Comparative Examples 4 and 5 show that when the BCIM photoinitiator or sensitizer is contained only, the composition can not be fundamentally cured.

In conclusion, when the compounds shown in the formulas (I) and (II) of the present invention are used as a sensitizer in combination with a photo-curing field and a photoinitiator, especially a diimidazole-based photoinitiator such as BCIM, And has a wide range of application prospects.

Examples of Photosensitive Resin Composition

Hereinafter, the present invention will be described in more detail by way of examples, but it should not be understood that the scope of protection of the present invention is limited. Also, unless otherwise stated, "part" and "%" are both on a mass basis.

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

&Lt; Synthesis of binder polymer (A-1) >

125 g of methacrylic acid as a copolymerization monomer, 275 g of methyl methacrylate and 100 g of styrene were mixed with 1.0 g of azobisisobutyronitrile to prepare solution a.

1.0 g of azobisisobutyronitrile is dissolved in a mixture of 60 g of methyl cellosolve and 40 g of toluene to prepare solution b.

400 g of a mixture having a mass ratio of methyl cellosolve and toluene of 6: 4 was introduced into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introducing tube, stirred while injecting nitrogen gas, Heat it.

The solution a is added dropwise to the flask for 4 hours, and the solution is kept at 80 ° C for 2 hours with stirring. Subsequently, the solution b is added dropwise to the solution in the flask for 10 minutes, and then the solution in the flask is kept at 80 DEG C for 3 hours with stirring. The solution in the flask is then heated to 90 DEG C for 30 minutes, kept at 90 DEG C for 2 hours and cooled to obtain a solution of the binder polymer (A-1).

The nonvolatile component (solid component) prepared by adding acetone to the solution of the binder polymer (A-1) was 50% by mass.

&Lt; Synthesis of Binder Polymer (A-2) >

125 g of methacrylic acid as a copolymerizable monomer, 25 g of methyl methacrylate, 125 g of benzyl methacrylate, and 225 g of styrene are mixed with azobisisobutyronitrile of 1.5 to prepare a solution c.

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

400 g of a mixture having a mass ratio of methyl cellosolve and toluene of 6: 4 was introduced into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introducing tube, stirred while injecting nitrogen gas, Heat it.

The solution c is dropped into the flask for 4 hours, and then the solution is kept at 80 DEG C for 2 hours with stirring. Then, the solution d is dropped into the solution in the flask for 10 minutes, and then the solution in the flask is kept at 80 DEG C for 3 hours with stirring. The solution in the flask is then heated to 90 DEG C for 30 minutes, kept at 0 DEG C for 2 hours and cooled to obtain a solution of the binder polymer (A-2).

The nonvolatile component (solid component) prepared by adding acetone to the solution of the binder polymer (A-2) was 50% by mass.

The weight average molecular weight of the binder polymer (A-1) is 60000 and the acid value is 163 mgKOH / g. The weight average molecular weight of the binder polymer (A-2) is 50000, and the acid value is 163 mgKOH / g. The weight average molecular weight was measured by gel permeation chromatography and converted to a standard polystyrene calibration curve. The conditions of GPC were as follows.

- GPC conditions

Pump: Model LC-20AD of Shimadzu Corporation, Japan; Chromatography column: GPC KF-803 (Shimadzu, Japan); Eluent: tetrahydrofuran; Measuring temperature: 25 占 폚; Flow rate: 1 mL / min; Detector: RID-10A.

&Lt; Preparation of Photosensitive Resin Composition >

The photosensitive resin compositions of Examples 27 to 30 and Comparative Example 6-9 were formulated in accordance with the ratios shown in Table 4. The numerical values in the table represent the number of components (on a mass basis). In addition, components (A) and (B) are masses calculated as solid components.

material Example
27 Example
28 Example
29 Example
30 Comparative Example
6 Comparative Example
7 Comparative Example
8 Comparative Example
9 A
A1 55 55 55 55 55 55 55 A2 55

B

B1 10 10 10 10 10 B2 10 10 10 B3 13 13 13 13 13 13 13 13 B4 10 10 10 10 10 10 10 10 B5 12 12 12 12 12 12 12 12 C C1 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7
D

D1 0.25 0.25 D2 0.25 D3 0.25 0.25 0.25 D4 0.25 0.25
adding
My Colorless
Crystal violet
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4 Malachite Green
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
solvent
Acetone 10 10 10 10 10 10 10 10 toluene 10 10 10 10 10 10 10 10 Methanol 10 10 10 10 10 10 10 10

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 mass% solution; A2: Methacrylic acid / methyl methacrylate / benzyl methacrylate / styrene = 25/5/25/45 (weight ratio), weight average molecular weight = 50,000, 50 mass% solution.

- (B) Photopolymerizable compound -

B1: compound represented by the general formula (I), those of n = 0, R ₉ is methyl; B2: trimethylolpropane trimethacrylate (TMPO); B3: 2,2-bis (4 - ((meth) acryloxypolyethoxy) phenyl) propane; B4: ethoxylated trimethylolpropane triacrylate (ETPTA); B5: Tri (methacryloyloxy-tetraethylene glycol-isocyanato-hexamethylene) isocyanurate.

- (C) Photopolymerization initiator -

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

- (D) Increasing dye -

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

<Preparation of Photosensitive Element>

The above photosensitive resin composition was uniformly applied to a polyethylene terephthalate film (Teijin Co., Ltd., product name: "HTF01") having a thickness of 16 탆, dried for 10 minutes through a hot air convection type dryer at 100 캜, To form a photosensitive resin layer having a film thickness of 10 mu m afterward.

A polypropylene protective film (product name: E200C, manufactured by Prince Paper Co., Ltd.) is adhered onto the photosensitive resin layer to obtain a photosensitive element in which a polyethylene terephthalate film (supporting film), a photosensitive resin layer and a protective film are sequentially laminated.

&Lt; Preparation of laminate &

A copper clad laminate (substrate, manufactured by Hitachi Chemical Co., Ltd .; product name: "Kagaku Kogyo Kogyo K.K.) ", which is a glass epoxy material in which copper foil having a thickness of 12 탆 was laminated on both surfaces thereof, MCL-E-67 ") is polished, rinsed, and then dried through an air stream. The polished copper clad laminate was heated to 80 DEG C, the protective film was peeled off, and the obtained photosensitive element was laminated in such a manner that the photosensitive resin layer was in contact with the copper surface. The lamination is carried out at a pressure of 0.40 MPa and a roll speed of 1.5 m / min using a hot roll at 110 캜.

Thus, a laminate in which a copper clad laminate, a photosensitive resin layer, and a supporting film were laminated successively was obtained. The obtained laminate was used as a test piece in the following test.

<Evaluation>

(Optical sensitivity measurement test)

A Hitachi 41-step stepwise exposure system was provided on the support film of the obtained test piece. Using a direct-writing type exposure apparatus (product name: Paragon-9000m, manufactured by Orbotech Ltd., Japan) using a semiconductor laser having a wavelength of 355 nm as a light source, Energy.

Then, the support film was peeled off, and an unexposed portion was removed by spraying a 1.0% by mass aqueous sodium carbonate solution at 30 캜 for 45 seconds to carry out development processing.

After the development processing, the number of stages of the step-type exposure system of the photocurable film formed on the copper clad laminate was measured to obtain an energy amount (mJ / cm ² ) having a step number of remaining steps of 17.0 stages after development. In the case of the photosensitivity of the photosensitive resin composition, the smaller the energy (mJ / cm ² ), the higher the photosensitivity, and the results are shown in Table 5.

(Evaluation of adhesion and resolution)

(Imaging) data of a wiring pattern having a line width / pore width of 5 / 5-47 / 47 (unit: 占 퐉) as a pattern for resolution evaluation was applied on a support film of the obtained test piece, Was exposed at an energy of 17.0 after the developing step. After the exposure, the same development processing as the above-described photosensitivity measurement test was performed.

After the developing treatment, the resist pattern was observed with an optical microscope. A resist pattern having a minimum gap width between line widths of the resist pattern formed without completely removing the void portion (unexposed portion) of the resist pattern and without causing twist or defect in the line portion (exposed portion) Mu m). The smaller the value, the better the adhesion and the resolution. The results are shown in Table 5.

(Evaluation of Tenting Reliability)

A circular hole having a diameter of 1 mm was formed on the copper clad laminate with a thickness of 0.4 mm at intervals of 7 mm, and the obtained photosensitive element was laminated on both sides thereof. The resulting photosensitive element was exposed to an energy amount of 17.0 Exposure was performed. After exposure, the same developing solution as in the light sensitivity measurement test was sprayed for 30 seconds to carry out development processing.

After development, the number (number) of the ruptured photosensitive elements in the total of 320 circular holes was measured, and the tenting rupture rate was calculated by the following equation, and the tent reliability was taken as follows. The results are shown in Table 5.

Tenting rupture rate = (number of hole ruptures / 320) * 100

Evaluation items Example
27 Example
28 Example
29 Example
30 Comparative Example
6 Comparative Example
7 Comparative Example
8 Comparative Example
9 Light sensitivity
(mJ / cm ² )
30
30
30
35
45
75
85
45 Adhesion (탆) 16 14 12 12 19 20 22 24 Resolution (탆) 16 14 12 12 19 20 22 24 Tent
Tear Ratio (%) 0 0 0 0 45 16 60 50

As shown in Table 5, the photosensitive element prepared with the photosensitive resin composition of Examples 27-30 exhibited significantly superior photosensitivity, tent reliability, adhesion and resolution, as compared with Comparative Example 6-9. In particular, although the (meth) acrylate compound having a skeleton derived from dipentaerythritol was used as the component (B) in Comparative Example 7, the short pyrazoline compound was not used as the sensitizing dye of the component (D) , The photosensitivity was worse and the reliability of the tenting was also worse than those of Examples 27 and 28.

As can be seen from the above, the photosensitive resin compositions of Examples 27 to 30 can form a printed circuit board excellent in light sensitivity, tent reliability, adhesion, and resolution in an etching process using a direct writing type exposure method.

[Examples 31-35]

In Examples 31-35, D5-D9 was used as the sensitizing dye of component (D), and D1 in Example 27 was substituted, and the other conditions were not changed. Thereafter, the photosensitive resin composition, the photosensitive element and the laminate were prepared by the method described in Example 27 and evaluated by the same method. The results are shown in Table 6.

D Example
31 Example
32 Example
33 Example
34 Example
35 D5 0.25 D6 0.25 D7 0.25 D8 0.25 D9 0.25 Light Sensitivity (mJ / cm ² ) 30 30 30 30 30 Adhesion (탆) 15 14 15 13 12 Resolution (탆) 15 14 15 13 12 Tenting rupture rate (%) 0 0 0 0 0

The structure of D5-D9 is as follows:

As shown in Table 6, when a pyrazoline (especially a compound corresponding to the general formula (I) or (II)) is used as the sensitizing dye, the photosensitive resin composition likewise exhibits excellent sensitivity, tent reliability, Respectively.

[Examples 36-39]

Examples 36-39 replaces B1 in Example 28 with B6-B9, respectively, and the other conditions remain unchanged. Thereafter, the photosensitive resin composition, the photosensitive element and the laminate were prepared by the method described in Example 28, and evaluated by the same method. The results are shown in Table 6.

B Example
36 Example
37 Example
38 Example
39 B6 10 B7 10 B8 10 B9 10 Light Sensitivity (mJ / cm ² ) 35 35 50 50 Adhesion (탆) 15 14 15 11 Resolution (탆) 15 14 15 11 Tenting rupture rate (%) 0 0 0 0

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

As shown in Table 7, even if the (meth) acrylate compound having a skeleton from dipentaerythritol is changed, the photosensitive resin composition is similarly subjected to the light sensitivity, tent reliability, , Adhesion and resolution were excellent.

From the above description, it can be seen that the embodiment of the present invention has realized the following technical effect.

The compound having the structure shown in the formula (I) or the formula (II) has excellent solubility, has an absorption band of 360 to 400 nm, and is used as a sensitizer in a system containing a photocurable system, particularly a diimidazole-based photoinitiator It is particularly suitable to be used, the effect of improving the photosensitivity is excellent, and the film to be produced also has good resolution and adhesion. In addition, since it contains an alkenyl group in the molecule or is a polymer compound, it is further characterized in that transition is not easily caused in the course of use.

The compound having the structure shown in the formula (I) or the formula (II) of the present application is excellent in solubility, and therefore, when used in combination with a binder polymer, a photopolymerizable compound having at least one ethylenically unsaturated bond and a photopolymerization initiator , It is possible to form a good dispersing effect with each component so that the action of each component can be fully exerted, thereby improving the sensitivity of the photosensitive resin composition and improving the resolution and adhesion of the film structure formed from the composition. The foregoing is merely a preferred embodiment of the present invention and is not to be construed as limiting the present invention. It will be apparent to those skilled in the art that various changes and modifications may be made therein. Any modifications, equivalent replacements, improvements, and so on, which are implemented within the spirit and principle of the present invention, are to be included within the scope of the present invention.

Claims (31)

As a pyrazoline sensitizer,
And has a structure represented by the following formula (I)

;
Or a pyrazoline sensitizer having a structure represented by the following formula (II):

,
Wherein R ₁ represents C ₁ -C ₁₀ straight or branched chain alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl, phenyl, substituted phenyl or C ₂ -C ₁₀ alkenyl; R ₂ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl; R ₃ represents a direct bond 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 substituent having a conjugated structure with the pyrazole ring; R ₆ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl; A is independently a repeating unit having a structure of -O- (CHR ₈ ) _m -, R ₈ is each independently selected from hydrogen, methyl or ethyl, m is an integer of 1-6; R ₇ has n external linkages and is selected from C ₁ -C ₆₀ straight or branched chain alkyl optionally with carbon or hydrogen thereof substituted by oxygen, sulfur or phenyl; n represents an integer of 1-20. The pyrazoline sensitizer according to claim 1, wherein R ₁ is selected from phenyl, substituted phenyl or C ₃ -C ₆ alkenyl. 3. A compound according to claim 1 or 2, wherein R &lt; _{1 &gt;} is C ₆ H ₅ *, CH ₃ C ₆ H ₄ *, CH ₃ CH ₂ C ₆ H ₄ *, CH ₃ CH ₂ H ₂ C ₆ H ₄ * 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 for _{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 * Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; The pyrazoline sensitizer according to claim 1, wherein R ₂ is hydrogen, C ₁ -C ₁₀ linear or branched alkyl. The pyrazoline sensitizer according to claim 1, wherein R ₄ is hydrogen, C ₁ -C ₁₀ linear or branched alkyl. The method of claim 1 wherein, R ₅ is phenyl, pyrrolyl, imidazolyl, carbazolyl, is selected from indolyl or alkenyl, optionally, these groups in the hydrogen atoms are each independently a C ₁ -C ₁₀ straight-chain or branched alkyl, a sensitizer pyrazoline-based, characterized in that which may be substituted by alkyl, cycloalkyl or cycloalkylalkyl, phenyl, or a heteroaryl group of C ₄ -C _10. 7. The pyrazoline sensitizer according to any one of claims 1 to 6, wherein R &lt; ₅ &gt; is selected from the following groups:

. The method of claim 1, wherein, R ₆ is hydrogen, a sensitizer pyrazoline-based, characterized in that is selected from linear or branched alkyl of C ₁ -C _6. The method of claim 1 or claim 8, wherein, R ₆ is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert- _{butyl, CH 3 C (CH 2 CH} 3) 2 - pyrazoline, characterized in that selected from sleepy A system of sensitization. The method of claim 1 wherein, A is _{- [O- (CHR 8) m} ] y - are selected from, that of the R ₈ are each independently selected from hydrogen or methyl, m is an integer of 1-3, y is 1-9. &Lt; / RTI &gt; The method of claim 1 or claim 10, wherein, A is _{- [OCH 2] y -,} - [OCH 2 CH 2] y -, - [OCH 2 CH 2 CH 2] y -, - [OCH (CH 3 ) -CH ₂ ] _y -, - [O-CH ₂ -CH (CH ₃ ) -CH ₂ ] _y -, wherein y represents an integer of 1-9. My. The pyrazoline sensitizer according to claim 1, wherein R ₇ is selected from the following groups:

. The pyrazoline sensitizer according to claim 1, wherein n is an integer of 1-8. A method for producing a sensitizer comprising the steps of:
(1) reacting the raw material a and the raw material b in a solvent containing a catalyst to produce an intermediate a;
(2) a step in which intermediate a and raw material c react under the action of strong alkali to produce intermediate b;
(3) deprotecting intermediate b under the action of an acid to obtain intermediate c;
(4) Intermediate c and raw material d are reacted in glacial acetic acid at 30-100 캜 for 2-20 h to produce intermediate d;
Wherein the sensitizer is represented by the formula (I)

Lt; / RTI &gt; structure,
(5) When R ₃ is a direct bond (empty), the intermediate d and the raw material e react in a solvent containing an acid-binding agent to produce a product; When R ₃ is -CH ₂ -CH (OH) -CH ₂ -O-, intermediate d and epichlorohydrin are reacted in a solvent containing a phase transfer catalyst, and after completion of the reaction, To continue the reaction to obtain an intermediate e; And then reacting the intermediate e and the starting material f with a catalyst in the presence of a polymerization inhibitor to obtain a product;
Wherein the sensitizer is represented by the formula (II)

Lt; / RTI &gt; structure,
(5) reacting intermediate d with methyl chloroacetate under the action of an acid-binding agent and a catalyst to obtain intermediate f;
(6) producing an intermediate product f and a starting material h by causing an ester exchange reaction under the action of a catalyst and a polymerization inhibitor;
The reaction procedure is as follows:

Raw material a raw material b intermediate a raw material c intermediate b

Intermediate c raw material d intermediate d

Raw material e product

Intermediate e raw material f product,
or

Raw material a raw material b intermediate a raw material c intermediate b

Intermediate c Material d Intermediate d Material g

Intermediate f raw material h product,
Wherein R ₁ represents C ₁ -C ₁₀ straight or branched chain alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl, phenyl, substituted phenyl or C ₂ -C ₁₀ alkenyl; R ₂ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl; R ₃ represents a direct bond (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 substituent having a conjugated structure with the pyrazole ring; R ₆ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl; A is independently a repeating unit having a structure of -O- (CHR ₈ ) _m -, R ₈ is each independently selected from hydrogen, methyl or ethyl, m is an integer of 1-6; R ₇ has n external linkages and is selected from C ₁ -C ₆₀ straight or branched chain alkyl optionally with carbon or hydrogen thereof substituted by oxygen, sulfur or phenyl; n represents an integer of 1-20. 15. The process according to claim 14, wherein in step (1), the catalyst is selected from methyl sulfonic acid, para toluenesulfonic acid, pyridinium para-toluenesulfonate. 15. The process for producing a sensitizer according to claim 14, wherein in step (2), the strong alkali is potassium hydroxide, sodium hydroxide or barium hydroxide. 15. The method for producing a sensitizer according to claim 14, wherein the deprotection in step (3) comprises dissolving the intermediate b in a hydrocarbon-based solvent containing an acid to proceed hydrolysis. The method of claim 14, wherein when the sensitizer has the structure of formula (I), in step (5), when R ₃ is directly bonded, the acid binding agent is selected from triethylamine, potassium carbonate, ethylenediamine, , And the solvent is selected from benzene, toluene, dichloromethane, and dichloroethane. 15. The process according to claim 14, wherein when the sensitiser has the structure of formula (I), when R ₃ is -CH ₂ -CH (OH) -CH ₂ -O- in step (5) Quaternary ammonium salt-based catalysts such as tetramethylammonium bromide, tetrabutylammonium bromide, tetrapropylammonium bromide, or alkaline catalysts such as dimethylimidazole, the strong alkali is sodium hydroxide and / or potassium hydroxide, the catalyst is selected from the group consisting of triphenylphosphine Pin, and the polymerization inhibitor is parahydroxyanisole. 15. The process according to claim 14, wherein the sensitizer has the structure of formula (II), wherein in step (5), the acid binder is pyridine, triethylamine or potassium carbonate and the catalyst is potassium iodide or sodium bromide Wherein the sensitizing agent is used as a sensitizer. 15. The method for producing a sensitizer according to claim 14, wherein, in the case where the sensitizer has the structure of the formula (II), the catalyst is a titanic acid compound in the step (6). The method according to claim 21, wherein the titanic acid compound is at least one compound selected from the group consisting of 2-ethylhexyl titanate, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra (2-ethylhexyl) Or a combination of two or more thereof. 23. The method of claim 22, wherein in step (6), the polymerization inhibitor is selected from the group consisting of parahydroxyanisole, N, N-diethylhydroxylamine, hydroquinone, catechol, para-tert- butylcatechol, methylhydroquinone, p-methoxyphenol, phenothiazine, and triphenylphosphine. 13. Use of the sensitizer according to any one of claims 1 to 13 in a photocuring composition. 25. An application according to claim 24, characterized in that said photocurable composition contains a diimidazole-based photoinitiator. As the photosensitive resin composition,
(A) a binder polymer; (B) a photopolymerizable compound having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) a sensitizing dye, wherein 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 binder polymer as claimed in claim 26, wherein the binder polymer as the component (A) is selected from one or more of acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin and phenol resin Wherein the photosensitive resin composition is a photosensitive resin composition. The photosensitive resin composition according to claim 26, wherein the content of the structural unit from the polymerizable monomer having a carboxyl group in the binder polymer (A) is 12-50 mass%. The photosensitive resin composition according to claim 26, wherein the component (B) comprises a (meth) acrylate compound having a skeleton derived from dipentaerythritol. The photosensitive resin composition according to claim 29, wherein the (meth) acrylate compound having a skeleton derived from dipentaerythritol has the structure shown in Formula (1)

In general formula (1)
In the general formula (1), R ₉ independently represents a hydrogen atom or a methyl group, A independently represents a C ₂ -C ₆ alkylene group, and n is an integer of 0-20. A photosensitive element and a laminate of the photosensitive resin composition according to any one of claims 26 to 30, a resist pattern production, an application in a printed circuit board and a lead frame production.