KR101477207B1 - Curable resin composition with good reliability - Google Patents

Abstract

More particularly, the present invention relates to a curable resin composition excellent in reliability, in which halide ion content is remarkably reduced, and a cured film having resistance to PCT, electroless plating resistance and heat resistance, which is important as a solder resist for a semiconductor package, A cured product thereof, a solder resist formed therefrom, and a printed circuit board having the cured film.

Description

[0001] Curable resin composition with good reliability [

More particularly, the present invention relates to a curable resin composition excellent in reliability, in which halide ion content is remarkably reduced, and a cured film having resistance to PCT, electroless plating resistance and heat resistance, which is important as a solder resist for a semiconductor package, A cured product thereof, a solder resist formed therefrom, and a printed circuit board having the cured film.

As a solder resist for a printed wiring board, a liquid type type developable solder resist, in which a pattern is formed by irradiating light such as ultraviolet rays and then developed and cured by heat and / or light, is mainstream. At present, a photo-solder resist that can be developed into an aqueous alkali solution due to environmental problems is mainly used in the production of actual printed wiring boards. In addition, in recent years, there has been a demand for increasing the density of printed wiring boards as electronic parts and electronic devices have become thinner and thinner. Accordingly, workability, high performance, and excellent reliability of a solder resist are also required.

However, conventional photo-solder resists that can be developed in an aqueous alkaline solution have problems in terms of durability and reliability, such as alkali resistance, water resistance, and heat resistance, which are lower than those of conventional solder resists capable of thermosetting and solvent development. The photo-solder resist which can be developed into an aqueous alkali solution has a hydrophilic group as a main component for developing an aqueous alkaline solution. However, due to the hydrophilic group, penetration of water and water vapor is easy and the chemical resistance is lowered and the adhesiveness between the solder resist film and copper is deteriorated have. Particularly, in semiconductor packages such as BGA and CSP, PCT resistance at high temperature and high humidity conditions is absolutely required. However, when voltage is applied under high temperature and high humidity conditions, defects are evaluated in HAST evaluation.

In addition, recently, the temperature tends to increase considerably during the package manufacturing process during the surface mounting process, and thus the inside / outside temperature of the package also tends to become remarkably high. In the conventional photosensitive solder resist, cracks Or there is a problem that the substrate or EMC is peeled off.

 As the carboxyl group-containing resin in the conventional solder resist, an epoxy acrylate-modified resin which is induced by the modification of the epoxy resin is generally used. For example, Japanese Patent Application Laid-Open No. 61-243869 discloses a solder resist composition comprising a photosensitive resin to which an acid anhydride is added to a reaction product of a novolac epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound. Japanese Patent Application Laid-Open No. 250012/1990 discloses a process for producing an epoxy resin obtained by adding acrylic acid to an epoxy resin obtained by reacting epichlorohydrin with a reaction product of salicylic aldehyde and monovalent phenol and then reacting the reaction product with an alkaline carboxylic acid or an anhydride thereof Discloses a solder resist composition comprising a photosensitive resin, a photopolymerization initiator, an organic solvent, and the like.

However, such conventional solder resist compositions are inferior in terms of resistance to PCT, as well as in HAST resistance and electrical insulation due to excessive halogen ions which are by-products in the process of manufacturing thermosetting components. Therefore, development of a curable resin composition having improved PCT resistance, HAST resistance, and electric insulation still needs to be developed.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide a photocurable, thermosetting resin composition and a cured product thereof capable of forming a cured film having excellent PCT resistance, electroless plating resistance and heat resistance, And a printed wiring board having the solder resist formed therefrom and the cured coating thereon.

(B) a photopolymerization initiator; (c) a reactive diluent containing an unsaturated double bond; (d) a thermosetting component, wherein the thermosetting component is a reactive diluent; wherein the halogen ion content of the thermosetting component is less than or equal to 0.05 wt% of the total amount of the component (d), (f) the halogen ion content of the filler is less than or equal to the total amount of the component (f) By weight of the thermosetting resin composition.

(B) a photopolymerization initiator; (c) a reactive diluent containing an unsaturated double bond; (d) a thermosetting component; (e) a thermosetting component; (1) (d) a process of mixing a thermosetting component with an aqueous solution of an alkali metal salt, and then separating the aqueous solution and the component (d) from the aqueous solution (F) independently of the above (1), (f) the filler is mixed with the purification solvent, and then the solvent and the component (f) (F) of the component (d) purified in (1) above and the component (f) purified in the above (2) after the halogen ion content is lowered to 50 ppm or less of the total amount of the component Is mixed with the remaining components to prepare a photocurable, thermosetting resin composition Is provided.

According to another aspect of the present invention, there is provided a solder resist obtained by applying the photocurable and thermosetting resin composition onto a substrate and drying the same.

According to another aspect of the present invention, there is provided a patterned cured product of the photo-curable, thermosetting resin composition.

According to another aspect of the present invention, there is provided a printed wiring board comprising the patterned cured film of the photo-curable, thermosetting resin composition.

According to the present invention, it is possible to obtain a photo-curable and thermosetting resin composition which is essentially required for a solder resist for a semiconductor package and has significantly improved resistance to PCT, heat resistance and HAST, and is particularly suitable for manufacturing a solder resist requiring high reliability Can be used.

Hereinafter, the present invention will be described in detail.

(a) a high heat resistant resin containing an unsaturated double bond and a carboxyl group

In the present invention, as the high heat-resistant resin containing (a) the unsaturated double bond and the carboxyl group, the softening point is preferably 60 ° C to 120 ° C, and more preferably 70 ° C to 110 ° C. If the softening point of the high heat-resistant resin is less than 60 캜, the heat resistance of the composition may be poor, which may deteriorate the heat resistance of the solder, and if it exceeds 120 캜, the viscosity may be too high during the resin production process.

The high heat-resistant resin of the present invention preferably contains a polymerization unit derived from phenol, cresol or a derivative thereof in order to secure high heat resistance. In order to achieve photo-curability, an unsaturated double bond derived from acrylic acid, methacrylic acid, And it is preferable to contain a carboxyl group derived from a polybasic acid anhydride such as phthalic anhydride or maleic anhydride to form a reaction group with excellent developability and a thermosetting part.

Specifically, a product obtained by reacting a phenolic hydroxyl group of a novolak resin derived from phenol, cresol or a derivative thereof with epichlorohydrin is reacted with a monocarboxylic acid containing an unsaturated double bond such as (meth) acrylic acid, and the resulting product (For example, SR90-B6T4 of KCC) obtained by reacting a polybasic acid anhydride such as maleic anhydride, maleic anhydride and phthalic anhydride with an unsaturated double bond and a carboxyl group can be used, but the present invention is not limited thereto.

The acid value of the high heat resistant resin (a) of the present invention is preferably 40 to 150 mgKOH / g, more preferably 50 to 130 mgKOH / g. If the acid value of the high heat-resistant resin (a) is less than 40 mgKOH / g, the developability of the aqueous alkali solution may deteriorate. If the acid value exceeds 150 mgKOH / g, the pattern line may be thinned during development with an aqueous alkaline solution, There may be a problem that it is difficult to form a normal pattern by dissolving and peeling off with an aqueous alkali solution without distinguishing the light portion.

The weight average molecular weight of the high heat resistant resin (a) of the present invention is preferably 2,000 to 150,000, more preferably 5,000 to 100,000. If the weight average molecular weight of the high heat-resistant resin (a) is less than 2,000, moisture resistance and reliability of the cured coating film may be lacked after exposure, and appearance change such as shrinkage upon development and low resolution may be caused. On the other hand, when the weight average molecular weight exceeds 150,000, developability and storage stability may be deteriorated.

In the resin composition of the present invention, the content of the high heat resistant resin (a) is preferably 20 to 60% by weight, more preferably 30 to 50% by weight, based on the total weight of the composition. If the content of the high heat resistant resin (a) in the composition is less than 20% by weight, the strength of the coating film may be lowered. If the content is more than 60% by weight, .

(b) Light curing Initiator

As the photopolymerization initiator (b) in the present invention, at least one selected from an oxime ester photopolymerization initiator, an? -Acetophenone photopolymerization initiator and an acylphosphine oxide photopolymerization initiator can be preferably used.

Specific examples of the oxime ester-based photopolymerization initiator include those of the following formula (1), more specifically those of the following formula (1-1) or (1-2) OXE-01 " or " IRGACURE OXE-02 ". These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more.

Wherein R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanol group having 2 to 20 carbon atoms or a benzoyl group, R ² is a phenyl group, An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanol group having 2 to 20 carbon atoms, or a benzoyl group)

(Wherein, R ⁹ denotes a hydrogen atom, a halogen atom, a carbon number of 1 - 12 alkyl group or an alkoxy group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzoyl group, or an alkyne having a carbon number of 2-12, playing; R ¹⁰ And R ¹² each independently represent a phenyl group, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanol group having 2 to 20 carbon atoms, or a benzoyl group; R ¹¹ is a hydrogen atom, , A cycloalkyl group having from 5 to 8 carbon atoms, an alkanol group having from 2 to 20 carbon atoms, or a benzoyl group)

Specific examples of the? -acetophenone-based photopolymerization initiator include those represented by the following formula (2), more specifically 2-methyl-1- [(4-methylthio) phenyl] -2- (4-morpholinyl) 2-benzyl-2- (dimethylamino) -4-morpholino butyrophenone, 2- (4-methylbenzyl) -2 - (dimethylamino) -1- (4-morpholinophenyl) butan-1-one. Examples of products include IRGACURE 907, IRGACURE 369 or IRGACURE 379 from BASF.

(Wherein R ³ and R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms; R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Together represent an alkyl ether group in the form of a ring)

Specific examples of the acylphosphine oxide photopolymerization initiator include those represented by the following formula (3), more specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-2,4,6-trimethylbenzoyl Phenyl-phosphine oxide, bis-2,4,4-trimethyl-benzyl-phosphine oxide, and IRGACURE TPO or IRGACURE 819 of BASF.

(Wherein R ⁷ and R ⁸ each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, a halogen atom, or an aryl group substituted with an alkyl group or an alkoxy group)

The amount of the photopolymerization initiator (b) to be used in the resin composition of the present invention is preferably 0.01 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, per 100 parts by weight of the high heat resistant resin (a). If the amount of the photopolymerization initiator (b) is less than 0.01 part by weight per 100 parts by weight of the high heat resistant resin (a), the photopolymerization may be insufficient and the coating film properties such as chemical resistance may be deteriorated. On the other hand, The absorption of light is increased, and thus the hardness of the core part may be lowered.

(c) a reactive diluent containing an unsaturated double bond

In the present invention, the reactive diluent (c) containing an unsaturated double bond is photo-cured by irradiation of active energy, and the high heat resistant resin (a) is insoluble in an aqueous alkali solution. That is, the reactive diluent (c) improves the strength of the cured coating film through photo-curing and improves heat resistance and reliability. As the reactive diluent (c), a compound containing 2-6 unsaturated double bonds in the skeleton can be used without any particular limitation, and the number of unsaturated double bonds can be selected according to the flexibility and strength of the desired cured coating film.

Specific examples of the reactive diluent (c) usable in the present invention include caprolactone acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dimethylpropane tetraacrylate, trimethyl At least one selected from the group consisting of propylene triacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and dipentaerythritol caprolactone acrylate, DPHA and DPCA-30 of Japanese explosives, and M200, M300 and M600 of Miwon Superior Company.

The amount of the reactive diluent (c) to be used in the resin composition of the present invention is preferably 5 to 100 parts by weight, more preferably 10 to 70 parts by weight per 100 parts by weight of the high heat resistant resin (a). If the amount of the reactive diluent (c) to be used is less than 5 parts by weight per 100 parts by weight of the high heat-resistant resin (a), the photocurability may deteriorate and pattern formation may become difficult due to the development of the alkali aqueous solution after irradiation of the activation energy. The solubility in an aqueous alkali solution may be lowered.

(d) a thermosetting component

In the present invention, the thermosetting component (d) is used for imparting heat resistance to the photocurable, thermosetting resin composition and the cured film of the present invention. As the thermosetting component (d), a compound having two or more epoxy groups or a ring-form thioether group in the molecule can be used. Specific examples thereof include a polyfunctional epoxy compound and a polyfunctional episulfide compound.

Examples of the polyfunctional epoxy compound include bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, brominated epoxy resin, halogen-free epoxy resin, novolak epoxy resin and biphenyl epoxy resin. Examples of bisphenol A epoxy resin products include JER828, JER834, JER1001, etc. of Japanese epoxy resin; Epikuron 840, Epikuron 850, Epikuron 1050 and the like manufactured by Dainippon Ink and Chemicals Industries, Ltd.; YD-011, YD-013, YD-127, YD-128 and the like of Togogasei; DER317, DER331, DER661, DER664 from Dow Chemical; ESA-011, ESA-014, ESA-115 and ESA-128 of BASF; AER330, AER331, AER661 and AER664 of Asahi Kasei Industries. Brominated epoxy resin products include JERYL903 from Japan Epoxy Resin; Epikuron 152, Epikuron 165 from Dainippon Ink and Chemicals, etc.; YDB-400, YDB-500 and the like of Togogasei; DER542 from Dow Chemical; And Alradido 8011 of BASF. Examples of the novolak-type epoxy resin products include JER152, JER154, etc. of Japanese epoxy resin; Epikuron N-730, Epikuron N-770, Epikuron N-865 and the like manufactured by Dainippon Ink and Chemicals Industries, Ltd.; YDCN-701, YDCN-704 and the like of Togogasei; DEN431 and DEN438 from Dow Chemical; Alludido ECN1235 of BASF, alaldido ECN1273, alaldido ECN1299 and the like; EPPN-201, EOCN-1020, EOCN-104S and RE-306 of Japanese explosives. However, it is not limited to the above-mentioned polyfunctional epoxy compound. These polyfunctional epoxy resins may be used alone or in combination of two or more. A novolak-type epoxy resin or a mixture thereof is preferably used.

Products of episulfide compounds having two or more ring-form thioether groups in the molecule include YL7000 of Japan Epoxy Resin, YSLV-120TE of Tokyo Kasei, and the like. It is also possible to use an episulfide resin in which the oxygen atom of the epoxy group of the novolac epoxy resin is replaced by a sulfur atom.

In the present invention, in order to improve the HAST (Highly Accelerated Stress Test) resistance of the photocurable and thermosetting resin composition, the halogen ion content of the thermosetting component (d) is 0.05% by weight or less of the total amount of the component (d) Is 0.03 wt% or less, and more preferably 0.01 wt% or less. If the halogen ion content of the thermosetting component (d) exceeds 0.05 wt% of the total amount of the component (d), there is a problem that the moisture absorption resistance of the resin composition is lowered and the electric insulating property is lowered due to the movement of metal ions such as Cu. In the high temperature and high humidity HAST condition, the water path is promoted due to the halogen ions remaining in the composition, which causes migration of Cu, which causes the electrical insulation property, which is a fundamental characteristic of the solder resist, to drop sharply. In the present invention, the HAST resistance of the resin composition can be remarkably improved by using the thermosetting component (d) and the filler (f) whose halogen ion content is controlled to a certain level or less.

According to a preferred embodiment of the present invention, the above-mentioned thermosetting component (d) is mixed with an aqueous solution of an alkali metal salt, and the purification step of separating the aqueous solution and the component (d) It can be lowered to 0.05 wt% or less of the total amount of the components. As the alkali metal salt aqueous solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or the like can be used, but the present invention is not limited thereto. The concentration of the alkali metal salt aqueous solution is generally 1 to 50% (w / v), and the purification step using the alkali metal salt aqueous solution is preferably 3 or more times (for example, 3 to 10 times) Is repeatedly performed five or more times (for example, five to ten times).

The amount of the thermosetting component (d) to be used in the resin composition of the present invention is preferably from 0.2 to 2.5 equivalents, more preferably from 0.3 to 2 equivalents, based on 1 equivalent of the high heat resistant resin (a). If a thermosetting component (d) of less than 0.2 equivalent per equivalent of the high heat-resistant resin (a) is used, carboxyl groups remain in the composition film and the heat resistance, alkali resistance, electrical insulation and the like are lowered. When the component (d) is used, the epoxy group or the ring-form thioether group remains in the dry film to lower the strength of the film and the like.

(e) Colorant

The photo-curable, thermosetting resin composition of the present invention comprises a colorant (e). As the coloring agent, pigments, dyes, pigments or coloring agents can be used, and from the viewpoint of environmental problems and human harmfulness, it is preferable that they do not contain a halogen. From the viewpoint of electric insulation, it is preferable not to contain metal ions (for example, Cu ions).

As the yellow colorant, azo, disazo, condensed azo, benzoimidazole, isoindolinone, and anthraquinone yellow colorants can be used.

Pigment Yellow 001, 002, 003, 004, 005, 006, 009, 010, 012, 061, 062, 065, 073, 074, 075, 097, 100, 104, 105, 111, 116, 1671, 169

Disazo system: Pigment Yellow 012, 013, 014, 016, 017, 055, 063, 081, 083, 087, 126, 127, 152, 170, 172, 174, 176, 188, 198

Condensation Ago system: Pigment Yellow 093, 094, 095, 128, 155, 166, 180

Benzoimidazole series: Pigment Yellow 120, 151, 154, 156, 175, 181

Isoindolinone: Pigment Yellow 109, 110, 139, 179, 185

Anthraquinone series: Pigment Yellow 163, 024, 108, 147, 193, 199, 222

As the blue colorant, a phthalocyanine-based or anthraquinone-based blue colorant can be used. Specific examples thereof are as follows:

Pigment Blue 15:00, 15:01, 15:02, 15:03, 15:04, 15:06, 16:00, 16:01, 60:00

In the case of a phthalocyanine-based blue colorant, when Cu ions are contained as shown in the following formula (4), Cu migration may occur under high temperature, high humidity and high voltage process conditions. The electrical insulation property, which is a fundamental characteristic of the solder resist, is deteriorated, which may lead to defective electric / electronic parts. Therefore, a phthalocyanine-based blue colorant not containing Cu ions is preferably used as represented by the following formula (5).

The amount of the colorant (e) to be used in the resin composition of the present invention is not particularly limited, and is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the high heat resistant resin (a).

(f) filler

The photocurable and thermosetting resin composition of the present invention includes a filler (f) to improve the physical strength and the like of the coating film. As the filler, a usual inorganic or organic filler can be used. Preferably, barium sulfate, nano silica, etc. can be used. In order to obtain a white appearance and flame retardancy, metal oxides such as titanium oxide, metal hydroxides such as aluminum hydroxide May be used.

In the present invention, the halogen ion content of the filler (f) is 50 ppm or less, more preferably 20 ppm or less of the total amount of the component (f) in order to improve the HAST (Highly Accelerated Stress Test) resistance of the photo- , And even more preferably 10 ppm or less. If the halogen ion content of the filler (f) exceeds 50 ppm of the total amount of the component (f), there is a problem that the moisture absorption resistance of the resin composition is lowered and the electric insulating property is lowered due to the movement of metal ions such as Cu. As described in the item (d) of the thermosetting component, halogen ions remaining in the composition weaken the HAST resistance. In the present invention, the thermosetting component (d) and the filler (f) The HAST resistance of the resin composition can be remarkably improved.

According to a preferred embodiment of the present invention, the purification process for separating the solvent and the component (f) is performed twice or more after the filler (f) is mixed with the purification solvent to adjust the halogen ion content to Of 50 ppm or less. There are no particular restrictions on the type of refining solvent, and deionized water is preferred. Preferably 100 to 500 parts by weight, more preferably 120 to 400 parts by weight, and even more preferably 150 to 300 parts by weight, of a purification solvent is used relative to 100 parts by weight of the filler (f) in one purification. If the amount of the refining solvent is too small, the purification efficiency is lowered, and the productivity may be lowered due to an increase in the entire process time. On the other hand, if the amount of the refining solvent is too large, it is not preferable because excessive water is generated. The purification process of the filler (f) with a refining solvent is preferably carried out at least 5 times (for example, 5 to 30 times), more preferably 10 times or more (for example, 10 to 30 times) (For example, 20 to 30 times).

The amount of the filler (f) to be used in the resin composition of the present invention is preferably 1 to 200 parts by weight, more preferably 10 to 150 parts by weight per 100 parts by weight of the high heat resistant resin (a). If the amount of the filler (f) is less than 1 part by weight per 100 parts by weight of the high heat resistant resin (a), the physical strength of the coating film may deteriorate. If the amount exceeds 200 parts by weight, viscosity of the composition increases, The cured product may become loose.

The photo-curable and thermosetting resin composition of the present invention may further contain, in addition to the above-mentioned components, other components such as a curing catalyst, a solvent and / or a defoaming agent, if necessary, within the range of achieving the object of the present invention .

As described above, in the present invention, the HAST resistance of the resin composition can be remarkably improved by using the thermosetting component (d) and the filler (f) in which the halogen ion content is adjusted to a certain level or less. (C) a reactive diluent containing an unsaturated double bond; (d) a thermosetting component; (c) a thermosetting component; and (d) a thermosetting component. (1) A process for producing a photo-curable, thermosetting resin composition comprising (e) a colorant and (f) a filler, wherein the thermosetting component is mixed with an aqueous solution of an alkali metal salt, (2) independently of (1) above, (f) mixing the filler with the purification solvent, and then mixing the solvent with (f (F) is reduced to 50 ppm or less of the total amount of the component (f), and the component (d) purified in the above (1) ) Is mixed with the remaining components to form a photocurable, thermosetting resin composition The method of manufacturing is provided for.

A method of obtaining the patterned cured coating film of the photocurable and thermosetting resin composition of the present invention is as follows. The composition is adjusted to an appropriate viscosity for application by using an organic solvent and applied on the substrate by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, or curtain coating, And the organic solvent contained in the composition is volatilized and dried at a temperature of 60 to 120 ° C. Thereafter, the resist pattern is selectively exposed to active energy through a photomask having a pattern formed by a contact or noncontact pattern, or a pattern is directly exposed by a laser direct exposure machine or the like, and the unexposed portion is developed with an aqueous alkali solution (0.1 to 3.0% aqueous solution of sodium carbonate) Thereby forming a pattern.

Examples of the substrate include a printed wiring board or a flexible printed wiring board on which circuits have been formed in advance, glass fibers impregnated with phenol resin, glass fibers impregnated with epoxy resin, glass fibers impregnated with bismaleimide triazine resin, copper clad laminate, polyimide film, A PET film, a glass substrate, a ceramic substrate, a wafer substrate, or the like. For the volatile drying performed after the resin composition is applied, a hot air circulating drying furnace, an infrared drying furnace, a hot plate, or the like can be used. Exposure devices used for irradiation of active energy include direct imaging devices (for example, a laser direct imaging device that directly expresses a pattern of a laser with a computer using CAD data), an exposure device equipped with a metal halide lamp, a (high) pressure mercury lamp A direct exposure apparatus using an ultraviolet lamp such as a high-pressure mercury lamp, or a (second) mounted exposure apparatus can be used. The range of the active energy is laser light and ultraviolet lamp light having a maximum wavelength of 340 to 420 nm, and both gas laser and solid laser can be used. As the developing method, a dipping method, a shower method, a spraying method, a brushing method or the like can be used. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, .

The photo-curable and thermosetting resin composition of the present invention can be used in the form of a dry film having a solder resist layer formed by applying a solder resist to a film such as polyethylene terephthalate and drying it, . The dry film is a structure in which a base film, a solder resist layer, and a peelable cover film to be used as needed are sequentially laminated. The solder resist layer is a layer obtained by applying a developable photo-curable and thermosetting resin composition to an alkali aqueous solution to a base film or a cover film and drying the same. A dry film can be obtained by laminating a cover film after forming a solder resist layer on a base film or forming a solder resist layer on a cover film and laminating a base film. As the base film, a thermoplastic film such as a polyester film having a thickness of 1 to 200 mu m is used. The solder resist layer is formed by uniformly applying a photocurable thermosetting resin composition to a base film or a cover film by a blade coater, a lip coater, a comma coater, a film coater or the like to a thickness of 5 to 200 탆 and drying the same. In the case of using a dry film, the cover film is peeled off, and the solder resist layer and the surface on which the circuit on the printed wiring board is formed are overlapped and laminated using a laminator to form a solder resist layer on the printed wiring board. When the exposure process, the development process, and the heat curing process are performed on the formed solder resist layer in the same manner as described above, a cured film can be obtained. The base film is peeled off before or after exposure.

Thus, according to another aspect of the present invention, there is provided a solder resist obtained by applying the photocurable and thermosetting resin composition of the present invention onto a substrate and drying the same; A patterned cured product of the photo-curable, thermosetting resin composition of the present invention; And a printed wiring board comprising the patterned cured film of the photo-curable, thermosetting resin composition of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to the following examples.

[ Example ]

Of the thermosetting component (d) Purification Example  One

200 g of a multifunctional epoxy resin (Printec, VG3101L, softening point: 65 캜, equivalent weight: 215, halogen ion content: 1.0248% by weight) was charged into a reactor equipped with a stirrer and stirred at 400 rpm for 30 minutes. Thereafter, 400 g of a 50% sodium hydroxide aqueous solution was added and the mixture was stirred at 600 rpm for 1 hour. After completion of the stirring, the mixture was allowed to stand for 1 hour to separate the aqueous solution and the resin portion, and the aqueous solution portion was removed. This purification process was repeated 5 times. After the completion of the final purification process, a pH adjusting agent was added to adjust the pH of the polyfunctional epoxy resin, and the remaining aqueous solution was removed by distillation under reduced pressure. The content of the halogen ion of the polyfunctional epoxy resin thus obtained was 0.0087% by weight and used as a thermosetting component (d-1) in the production of the resin composition.

Of the thermosetting component (d) Purification Example  2

200 g of a multifunctional epoxy resin (Printec, VG3101L, softening point: 65 캜, equivalent weight: 215, halogen ion content: 1.0248% by weight) was charged into a reactor equipped with a stirrer and stirred at 400 rpm for 30 minutes. Thereafter, 400 g of a 25% sodium hydroxide aqueous solution was added, and the mixture was stirred at 600 rpm for 2 hours at high speed. After completion of the stirring, the mixture was allowed to stand for 1 hour to separate the aqueous solution and the resin portion, and the aqueous solution portion was removed. This purification process was repeated 5 times. After the completion of the final purification process, a pH adjusting agent was added to adjust the pH of the polyfunctional epoxy resin, and the remaining aqueous solution was removed by distillation under reduced pressure. The content of the halogen ion of the multifunctional epoxy resin thus obtained was 0.0183% by weight and used as a thermosetting component (d-2) in the production of the resin composition.

Of the thermosetting component (d) Comparative Purification Example  One

200 g of a multifunctional epoxy resin (Printec, VG3101L, softening point: 65 캜, equivalent weight: 215, halogen ion content: 1.0248% by weight) was charged into a reactor equipped with a stirrer and stirred at 400 rpm for 30 minutes. Thereafter, 400 g of a 50% sodium hydroxide aqueous solution was added and the mixture was stirred at 600 rpm for 1 hour. After completion of the stirring, the mixture was allowed to stand for 1 hour to separate the aqueous solution and the resin portion, and the aqueous solution portion was removed. The pH of the polyfunctional epoxy resin was adjusted by repeating the purification process without adding the pH adjusting agent, and the residual aqueous solution was removed by distillation under reduced pressure. The content of the halogen ion of the polyfunctional epoxy resin thus obtained was 0.3521% by weight and used as a thermosetting component (d-3) in the production of the resin composition.

Of the thermosetting component (d) Comparative Purification Example  2: Not refined

(Printec, VG3101L, softening point: 65 占 폚, equivalent weight: 215, halogen ion content: 1.0248% by weight) was used as a thermosetting component (d-4) for the preparation of the resin composition.

filler  (f) Purification Example  One

100 g of barium sulfate (Sakai, B-30, d50 = 0.3 mu m, halogen ion content: 198 ppm) was added to the reactor equipped with a stirrer and stirred at 500 rpm for 1 hour. Thereafter, 250 g of deionized water was added and stirred at 700 rpm for 2 hours. After completion of the stirring, the mixture was allowed to stand for 1 hour, and the mixture was separated into a barium sulfate portion and a deionized water layer, and the deionized water layer was removed. This purification process was repeated 20 times. After completion of the final purification step, the halogen ion content of barium sulfate analyzed by ion chromatography was 9 ppm, which was used as a filler (f-1) in the preparation of the resin composition.

filler  (f) Purification Example  2

100 g of barium sulfate (Sakai, B-30, d50 = 0.3 mu m, halogen ion content: 198 ppm) was added to the reactor equipped with a stirrer and stirred at 500 rpm for 1 hour. 150 g of deionized water was then added and the mixture was stirred at 700 rpm for 2 hours. After completion of the stirring, the mixture was allowed to stand for 1 hour, and the mixture was separated into a barium sulfate portion and a deionized water layer, and the deionized water layer was removed. This purification process was repeated 20 times. After completion of the final purification step, the halogen ion content of barium sulfate analyzed by ion chromatography was 25 ppm, which was used as a filler (f-2) in the preparation of the resin composition.

filler  (f) Comparative Purification Example  One

100 g of barium sulfate (Sakai, B-30, d50 = 0.3 mu m, halogen ion content: 198 ppm) was added to the reactor equipped with a stirrer and stirred at 500 rpm for 1 hour. Thereafter, 250 g of deionized water was added and stirred at 700 rpm for 2 hours. After completion of the stirring, the mixture was allowed to stand for 1 hour, and the mixture was separated into a barium sulfate portion and a deionized water layer, and the deionized water layer was removed. The halogen ion content of barium sulfate analyzed by ion chromatography was 127 ppm, and the purification process was not repeated, and this was used as a filler (f-3) in the production of a resin composition.

filler  (f) Comparative Purification Example  2: Not refined

Barium sulfate (Sakai, B-30, d50 = 0.3 탆, halogen ion content: 198 ppm) which had not been purified was used as a filler (f-4).

Resin composition manufacturing Example  1 to 3 and Comparative Example  1-3

The thermosetting components (d-1) to (d-4) and the fillers (f-1) to (f-4) and the raw material components shown in the following Table 1 were compounded in the ratios (parts by weight) shown in Table 1, The mixture was preliminarily mixed through a stirrer and dispersed with a 3 roll mill, and viscosity correction was carried out to prepare a photocurable thermosetting resin composition. The degree of dispersion of the prepared photo-curing and thermosetting resin composition was evaluated by a grindmeter, and as a result, it was 10 탆 or less.

In addition, halogen ion content was analyzed using Prasco combustion process ion chromatography according to JPCA standard, which is a reference standard, for the photocurable and thermosetting resin composition. The results of the analysis are shown in Table 2 below.

The photo-curable and thermosetting resin compositions of the prepared examples and comparative examples were evaluated for their properties as follows.

Sensitivity

After the surface of the circuit pattern substrate was subjected to washing and washing and drying, the photocurable and thermosetting resin compositions of Examples and Comparative Examples were applied to the entire surface by screen printing and dried at 80 ° C for 30 minutes Thickness: about 25 占 퐉). After the drying, the exposure process was carried out with a 21-step tablet (manufacturer: Kodak) using an exposure apparatus equipped with a high-pressure mercury lamp. After exposure, the substrate was developed with a 1% aqueous solution of sodium carbonate at 30 DEG C for 90 seconds. Optimum exposure conditions were selected based on the sensitivity of the step tablet (sensitivity = 6).

Developing margin

The photo-curable and thermosetting resin compositions of Examples and Comparative Examples were applied on a substrate by screen printing, dried at 80 ° C, taken out at intervals of 10 minutes from 30 minutes to 100 minutes, and cooled at room temperature. Thereafter, development was carried out for 90 seconds with a 1% aqueous solution of sodium carbonate at 30 DEG C, and the maximum allowable drying time at which no residue remained was defined as a developing margin.

Resolution

The photo-curable and thermosetting resin compositions of Examples and Comparative Examples were applied onto a substrate by screen printing, dried at 80 DEG C for 30 minutes, and cooled at room temperature. A pattern mask film was pressed on the substrate, exposed at 200 mJ / cm ² through an exposure device equipped with a high-pressure mercury lamp, developed with a 1% aqueous sodium carbonate solution at 30 캜 for 90 seconds, and washed with water to form a pattern. The size of the formed pattern was measured to make it resolution.

Adhesion ( tackiness )

The photo-curable and thermosetting resin compositions of Examples and Comparative Examples were applied onto a substrate by screen printing, dried at 80 DEG C for 30 minutes, and cooled at room temperature. A film for pattern mask made of polyester was pressed on this substrate for 1 minute, and when the film for pattern mask was peeled off, the tackiness was evaluated according to the following criteria.

○: No transfer when peeling off the film

?: When the film is peeled off, there is a part of the transfer, and a minute force is required when peeling off

X: When the film is peeled, there is a transfer, and force is required when peeling off

Solder heat resistance

The photo-curable, thermosetting resin compositions of Examples and Comparative Examples were applied on a substrate by screen printing, dried at 80 DEG C for 30 minutes, and cooled at room temperature. After exposure of this substrate to 200mJ / cm ² through an exposure machine with a high pressure mercury lamp is, it was exposed by further 1100mJ / cm ^2. Thereafter, the mixture was heated at 150 DEG C for 60 minutes to complete the final curing. The thus obtained substrate was immersed in a solder bath set at 260 DEG C for 10 seconds. The immersion step was repeated three times. At this time, solder heat resistance was evaluated based on the following criteria on the basis of appearance change and peeling of the solder resist layer observed by naked eyes.

○: No external change and peeling

DELTA: Micro-contour change and micro-exfoliation

X: Existence change is severe and film peeling exists

PCT  ( Pressure Cooker Test )

The substrate produced through the above process was treated under the conditions of a temperature of 121 占 폚, a humidity of 100%, a pressure of 2 atm, and a time of 168 hours by using a PCT equipment (manufacturer: Ileatech, model name: PCT-80) The conditions were evaluated according to the following criteria.

○: No external change, discoloration, or leaching

DELTA: Microstructure change, some discoloration and elution

X: Excessive change in appearance, excessive discoloration and dissolution

HAST  ( Highly Accelerated Stress Test )

An evaluation substrate was prepared on the BT substrate on which the electrode (line space: 30 mu m) was formed based on the above-described process. A voltage of 5 V was applied to the substrate under a high-temperature and high-humidity condition having a temperature of 130 캜 and a humidity of 85%, and HAST evaluation was performed for 168 hours. After 168 hours, the insulation resistance was evaluated according to the following criteria.

○: more than 10 ⁸ Ω

Δ: 10 ⁶ to 10 ⁸ Ω

X: Less than 10 ⁶ Ω

The results of the above characteristics evaluation are shown in Table 3 below.

Preparation and evaluation of dry film

The photo-curable and thermosetting resin compositions of the examples and comparative examples were diluted with methyl ethyl ketone and then applied onto a PET film made of a polyester material and dried at 80 캜 for 30 minutes to form a solder resist layer having a thickness of 25 탆. And a cover film was laminated thereon to prepare a dry film. By peeling off the cover film from the prepared dry film and laminating the film on the substrate, exposed to 200mJ / cm ² after the high-pressure mercury lamp through an exposure system is mounted, such as the process after it was exposed by further 1100mJ / cm ^2. Thereafter, the mixture was heated at 150 DEG C for 60 minutes to complete the final curing. The characteristics of the above items were evaluated for the substrate thus obtained, and the results are shown in Table 4 below.

Claims (15)

(a) a heat-resistant resin containing an unsaturated double bond and a carboxyl group, (b) a photopolymerization initiator, (c) a reactive diluent containing an unsaturated double bond, (d) a thermosetting component, In producing a photocurable and thermosetting resin composition,
(1) The purification process of (d) mixing the thermosetting component with an alkali metal salt aqueous solution and separating the aqueous solution and the component (d) is carried out twice or more to lower the halogen ion content to 0.05% by weight or less of the total amount of the component ,
(2) The purification process for separating the solvent and the component (f) is performed twice or more after the filler is mixed with the purification solvent, independently of the above (1) After lowering to 50ppm or less,
A method for producing a photocurable thermosetting resin composition by mixing the component (d) purified in (1) and the component (f) purified in (2) The method for producing a photocurable thermosetting resin composition according to claim 1, wherein the heat-resistant resin (a) containing an unsaturated double bond and a carboxyl group comprises a polymerization unit derived from phenol, cresol or a derivative thereof. The photocurable thermosetting resin composition according to claim 1, wherein the photopolymerization initiator (b) is at least one selected from an oxime ester photopolymerization initiator, an? -Acetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator ≪ / RTI > The composition of claim 1, wherein the reactive diluent (c) is selected from the group consisting of caprolactone acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dimethylpropane tetraacrylate, trimethylpropanol triacryl Characterized in that it is at least one selected from the group consisting of tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and dipentaerythritol caprolactone acrylate. A method for producing a resin composition. The method for producing a photocurable thermosetting resin composition according to claim 1, wherein the thermosetting component (d) is at least one selected from a polyfunctional epoxy compound and a polyfunctional episulfide compound. The method for producing a photocurable, thermosetting resin composition according to claim 1, wherein the step of refining the thermosetting component (d) is repeated at least five times. The method for producing a photocurable, thermosetting resin composition according to claim 1, wherein the colorant (e) contains no halogen and no metal ion. The method for producing a photocurable thermosetting resin composition according to claim 1, wherein the filler (f) is at least one selected from barium sulfate, nano silica, metal oxides and metal hydroxides. The method for producing a photocurable, thermosetting resin composition according to claim 1, wherein the step of purifying the filler (f) is repeated 20 times or more. delete delete delete delete delete delete