KR20150027381A - Photosensitive resin composition with good reliability and method for preparing the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition with good reliability and a manufacturing method thereof and, more specifically, a photo-curable thermosetting resin composition which has a pressure cooler test (PCT) resistance for semiconductors, highly accelerated stress test (HAST) resistance, electroless gold plating resistance and heat impact resistance as a solder resist while forming excellent cured films, a manufacturing method thereof, a dry film and cured article thereof and a printed wiring board made by forming a cured film like a solder resist with use thereof.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a photosensitive resin composition,

The present invention relates to a photosensitive resin composition having excellent reliability and a method for producing the same, and more particularly, to a solder resist for a semiconductor package which has excellent PCT resistance, HAST resistance, electroless gold plating resistance and heat shock resistance, Which is capable of forming a cured film, a process for producing the same, a dry film and a cured product thereof, and a cured film such as a solder resist formed thereon.

Currently used solder resists for semiconductor package substrates are required to have high resolution, high performance, and high reliability. Particularly, resistance to high temperature and high humidity conditions is required for securing high reliability. For example, stress relieving stress applied to solder resist in PCT (Pressure Cooker Test), HAST (High Accelerated Stress Test) and TC Technology is essential. In addition, solder resists must be stress-relieved and flexible in accordance with the tendency of thinning and shortening of semiconductor package. In addition, there is a need for a technique capable of preventing Cu migration of copper patterns in circuit boards under high temperature and high humidity conditions.

In the conventional solder resist, there is an example in which reliability is secured by using a butadiene-modified epoxy resin as a stress relaxation agent (Korean Patent Laid-Open Nos. 10-2012-0022820 and 10-2011-0102193) It is disadvantageous in that it is difficult to control the degree of reactivity of the entire solder resist composition because heat resistance may be deteriorated depending on the glass transition temperature sensitivity.

On the other hand, an inorganic filler is generally used for a photosensitive resin composition used for a printed circuit board in order to improve heat resistance and reliability. In order to exhibit excellent heat resistance and weatherability by mixing such an inorganic filler in a raw material, need.

A roll mill is used to disperse an inorganic filler in a raw material in the production of a conventional photosensitive resin composition. The physical properties and degree of dispersion of the inorganic filler vary depending on the resin composition, And there are difficulties in quality control and process control.

When the photosensitive resin composition is prepared using a roll mill according to the conventional art as described above, a long time is required for the production of the photosensitive resin composition, which results in a reduction in the production yield, which results in a decrease in production efficiency. In addition, the roll mill is disadvantageous in that the products are exposed to the outside during the dispersion process, and there is a high risk of safety risk in the work.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a cured coating film having excellent flexibility while securing PCT resistance, HAST resistance, electroless gold plating resistance, And to provide a printed circuit board in which a cured film such as a solder resist is formed by the dry film and the cured product thereof.

Another object of the present invention is to provide a highly desirable method for increasing the production amount, improving the quality stabilization, and reducing the cost, by shortening the production time in the production of the photosensitive resin composition.

(2) a photopolymerization initiator; (3) a reactive diluent containing an unsaturated double bond; (4) a thermosetting component; and (4) a thermosetting component. (5) a filler, (6) an ion adsorbent, and (7) a core shell particle type elastomer and a silicone elastomer.

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

According to still another aspect of the present invention, there is provided a solder resist dry film obtained by applying the photocurable thermosetting resin composition to a base film and drying the base film.

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

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

According to another aspect of the present invention, there is provided a process for producing the photo-curable thermosetting resin composition, comprising the steps of: (1) mixing a primary raw material mixture containing a high heat resistant resin containing an unsaturated double bond and a carboxyl group, Wet mixing in a mixer; (2) dispersing and mixing the wet mixture obtained in the step (1) using a bead mill; And (3) adding a second raw material mixture containing a photopolymerization initiator to the dispersion mixture obtained in the step (2) and stirring and mixing the mixture.

By using the photo-curable thermosetting resin composition of the present invention, it is possible to form a cured film excellent in flexibility while ensuring PCT resistance, HAST resistance, electroless gold plating resistance and heat shock resistance which are important as solder resist for semiconductor packages.

In addition, when the photocurable thermosetting resin composition is produced according to the preferred method disclosed in the present invention, the production time can be shortened to increase the production amount, to improve the quality stabilization, and to obtain the cost saving effect.

Hereinafter, the present invention will be described in more detail.

One. Photocurable  Thermosetting resin composition

The photo-curable thermosetting resin composition of the present invention comprises (1) a high heat-resistant resin containing an unsaturated double bond and a carboxyl group, (2) a photopolymerization initiator, (3) a reactive diluent containing an unsaturated double bond, (4) , (5) a filler, (6) an ion adsorbent, and (7) a core shell particulate elastomer and a silicone elastomer.

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

The high heat-resistant resin containing an unsaturated double bond and a carboxyl group is preferably derived from phenol or cresol or a derivative thereof capable of securing high heat resistance, and the softening point is preferably 60 ° C to 120 ° C, More preferably 110 < 0 > C. If the softening point of the high heat-resistant resin containing an unsaturated double bond and a carboxyl group is less than 60 캜, the heat resistance of the composition becomes poor and it may lead to defects in heat resistance such as solder heat resistance. If it exceeds 120 캜, It may lead to a lack of workability and a decrease in yield.

In the high heat-resistant resin, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof (e.g., acrylate or methacrylate). The high heat-resistant resin preferably contains a carboxyl group to form a reaction group with excellent developability and a thermosetting part, and it is preferably derived from a polybasic acid anhydride such as phthalic anhydride or maleic anhydride.

In the present invention, specific examples of the high heat resistant resin having an unsaturated double bond and a carboxyl group include a product obtained by reacting a phenolic hydroxyl group of a novolac resin of phenol or cresol or a derivative thereof with epichlorohydrin and adding an unsaturated double bond such as (meth) And then reacting the resultant product with a polybasic acid anhydride such as maleic anhydride or phthalic anhydride.

The acid value of the high heat-resistant resin is preferably from 40 to 150 mgKOH / g, more preferably from 50 to 130 mgKOH / g. If the acid value of the high heat-resistant resin is less than 40 mgKOH / g, developability due to the alkali aqueous solution may be lacking. If the acid value exceeds 150 mgKOH / g, the pattern line may be thinned due to development with an aqueous alkali solution, It is possible to dissolve and peel off an alkali aqueous solution without distinguishing the exposed portions, making it difficult to form a normal pattern.

The weight average molecular weight of the high heat resistant resin varies depending on the skeleton of the base resin, but is preferably from 2,000 to 150,000, more preferably from 5,000 to 100,000. If the weight average molecular weight is less than 2,000, moisture resistance and reliability of the cured coating film after exposure may be lacked, and appearance change such as shrinkage upon development and low resolution may be caused. On the other hand, if the weight average molecular weight exceeds 150,000, the developability is significantly lowered and the storage stability is lowered.

The blending amount of the high heat resistant resin is 20-60 wt%, preferably 30-50 wt%, based on the total weight of the composition. If the blending amount of the high heat-resistant resin is less than 20% by weight of the total weight of the composition, the strength of the coating film is lowered, which is undesirable. When the blending amount is more than 60% by weight, It is not preferable.

(2) Light curing Initiator

As the photopolymerization initiator, it is preferable to use at least one selected from an oxime ester photopolymerization initiator, an? -Acetophenone photopolymerization initiator and an acylphosphine oxide photopolymerization initiator. Exemplary structures of these photopolymerization initiators are shown below.

In the above structural formula (1), R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 5-8 carbon atoms, an alkanol or a benzoyl group having 2-20 carbon atoms; R ² represents a phenyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkanol or benzoyl group having 2 to 20 carbon atoms.

In the structural formula (2), 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 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl ether in the form of a ring in which two are bonded.

In the above formula (3), R ⁷ and R ⁸ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group having 6 to 12 carbon atoms, a halogen atom, An aryl group substituted with an alkoxy group.

Representative oxime ester photopolymerization initiators represented by the structural formula (1) include compounds represented by the following structural formulas (4) and (5).

In the above structural formula (5), R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzoyl group, an alkanol group having 2 to 12 carbon atoms or an alkoxy group; R ¹⁰ represents a phenyl group, an alkyl group having 1-12 carbon atoms, an alkanol group having 2-20 carbon atoms and a cycloalkyl group having 2-20 carbon atoms, or a benzoyl group; R ¹¹ 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 or a benzoyl group having 2 to 20 carbon atoms; R ¹² represents a phenyl group, an alkyl group having 1 to 12 carbon atoms, an alkanol group having 2 to 20 carbon atoms and a benzoyl group having 5 to 8 carbon atoms.

Examples of the oxime ester photopolymerization initiator of the structural formula (1) include IRGACURE OXE-01 and IRGACURE OXE-02 from BASF. These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more.

Representative a-acetophenone-based photopolymerization initiators represented by the structural formula (2) include 2-methyl-1 - [(4-methylthio) phenyl] -2- (4-morpholinyl) 2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like. have. Examples of such products of the? -Acetophenone photopolymerization initiator include IRGACURE 907, IRGACURE 369 or IRGACURE 379 from BASF.

Representative acylphosphine oxide-based photopolymerization initiators represented by the structural formula (3) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-2,4,6-trimethylbenzoyl-phenylphosphine oxide, bis- 2,4,4-trimethyl-benzyl-phosphine oxide, and the like. Products of such acylphosphine oxide photopolymerization initiators include IRGACURE TPO or IRGACURE 819 from BASF.

The blending amount of the photopolymerization initiator is preferably from 0.01 to 30 parts by mass, more preferably from 0.5 to 15 parts by mass, per 100 parts by mass of the high heat-resistant resin containing (1) the unsaturated double bond and the carboxyl group. When the blending amount of the photopolymerization initiator is less than 0.01 part by mass based on 100 parts by mass of the above (1) high heat-resistant resin, photo-curing is insufficient and the coating film characteristics such as peeling off or chemical resistance are deteriorated. The absorption of light at the surface is increased and the deep curing property is accordingly lowered, which is not preferable.

(3) a reactive diluent containing an unsaturated double bond

The reactive diluent containing an unsaturated double bond used in the present invention is photo-cured by irradiation with active energy and insolubilizes the above (1) high heat-resistant resin containing an unsaturated double bond and a carboxyl group in an aqueous alkaline solution. In addition, it has the effect of improving the strength of the cured coating film through light curing and improving the heat resistance and reliability. Such a reactive diluent is not particularly limited as long as it is a compound containing, for example, 2-6 unsaturated double bonds in the skeleton. However, depending on the number of unsaturated double bonds, the flexibility and strength of the cured coating film and the reliability of the composition are different .

Specific examples of the reactive diluent containing an unsaturated double bond are as follows: caprolactone acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dimethylpropane tetraacrylate, Trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, dipentaerythritol caprolactone acrylate, and the like.

Examples of the products of the reactive diluent include DPHA, DPCA-30, and M200, M300, and M600 of Miwa Chemical Co., Ltd., which are Japanese explosives.

The amount of the reactive diluent is preferably 5-100 parts by weight, more preferably 10-70 parts by weight, per 100 parts by weight of the high heat-resistant resin containing (1) the unsaturated double bond and the carboxyl group. When the blending amount of the reactive diluent is less than 5 parts by mass based on 100 parts by mass of the high heat resistant resin (1), photo-curability is deteriorated and pattern formation becomes difficult due to development with an aqueous alkaline solution after irradiation of active energy, When the amount is larger than the above-mentioned range, the solubility in an aqueous alkali solution is deteriorated.

(4) Thermosetting component

In the present invention, a thermosetting component is used to impart heat resistance to the photocurable thermosetting resin composition. As the thermosetting component, a general thermosetting component such as a block isocyanate compound, a benzoxazine resin, a cyclocarbonate compound, a polyfunctional epoxy compound, or a polyfunctional oxetane compound can be used. Preferably, a compound having two or more ring-shaped ether groups or thioether groups in the molecule as the thermosetting component can be used.

Examples of the compound having two or more ring-shaped ether groups in the molecule include compounds having two or more epoxy groups in the molecule, i.e., polyfunctional epoxy compounds, and compounds having two or more thioether groups in the molecule Examples include multifunctional episulfide compounds.

Examples of the polyfunctional epoxy compound include bisphenol A multifunctional epoxy resin, bisphenol F multifunctional epoxy resin, hydrogenated bisphenol A multifunctional epoxy resin, brominated multifunctional epoxy resin, halogen-free multifunctional epoxy resin, novolak multifunctional epoxy resin, biphenyl Polyfunctional epoxy resins, and the like. Bisphenol A multifunctional epoxy resin products include JER828, JER834, JER1001; Epikuron 840, Epikuron 850, Epikuron 1050 from Dai-Nippon Ink Chemical Industry; YD-011, YD-013, YD-127, and YD-128 of Tokyo Kasei; DER317, DER331, DER661, DER664 from Dow Chemical; BASF's ESA-011, ESA-014, ESA-115, ESA-128; AER330, AER331, AER661, AER664 of Asahi Kasei Industries; . Brominated multifunctional epoxy resin products include JERYL903 from Japan Epoxy Resin; Epikuron 152, Epikuron 165 from Dai-Nippon Ink Chemical Industry; YDB-400, YDB-500 from Tokuga Seis; DER542 from Dow Chemical; Aladdido 8011 of BASF; . Novaled-type multi-functional epoxy resin products include JER152, JER154; Epikuron N-730, Epikuron N-770, Epikuron N-865 from Dai-Nippon Ink Chemical Industry; YDCN-701, YDCN-704; DEN431 and DEN438 from Dow Chemical; Alludido ECN1235 of BASF, alaldido ECN1273, alaldido ECN1299; EPPN-201, EOCN-1020, EOCN-104S, RE-306 of Japanese explosives; . However, it is not limited to the above-mentioned multifunctional 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.

Examples of the episulfide compound having two or more ring-form thioether groups in the molecule include YL7000 of Japan Epoxy Resin; YSLV-120TE by Tokugasei; . An episulfide resin in which the oxygen atom of the epoxy group of the Novolak type epoxy resin is replaced with a sulfur atom can also be used.

The blending amount of the above-mentioned thermosetting component preferably falls between 0.6 and 2.5 equivalents, more preferably between 0.8 and 2.0 equivalents, relative to 1 equivalent of the above (1) high heat-resistant resin containing an unsaturated double bond and a carboxyl group. If the equivalence of the thermosetting component to one equivalent of the above (1) high heat-resistant resin is less than 0.6, it is not preferable because a carboxyl group is left in the composition film and the heat resistance, alkali resistance and electric insulation property are lowered. (Thio) ether group in the form of a ring having a molecular weight remains in the dried coating film and the strength or the like of the coating film is lowered.

(5) filler

The photocurable thermosetting resin composition of the present invention includes a filler to increase the physical strength and the like of the coating film. An inorganic filler or an organic filler can be used as the filler, and inorganic fillers such as barium sulfate and nano silica are particularly preferably used. In order to obtain a white appearance and flame retardancy, metal oxides such as titanium oxide and metal hydroxides such as aluminum hydroxide can be used as fillers.

The amount of the filler to be blended is preferably 200 parts by mass or less, for example, 0.1-150 parts by mass, more preferably 1-100 parts by mass (parts by mass) relative to 100 parts by mass of the high heat-resistant resin containing (1) the unsaturated double bond and the carboxyl group. to be. When the amount of the filler is more than 200 parts by mass based on 100 parts by mass of the above (1) high heat-resistant resin, the viscosity of the composition is increased, resulting in lack of workability and deterioration of printing property or curing of the cured product.

(6) Ion adsorbents

The photo-curable thermosetting resin composition of the present invention comprises an ion adsorbent to inhibit the occurrence of ion migration in the cured film over a long period of time under high-temperature and humid conditions without inhibiting viscosity increase and adhesion. It is considered that this is due to the property that an ion adsorbent (for example, metal hydroxide) acts as an anion exchanger under acidic conditions. In other words, it is generally known that the copper circuit under high-temperature humidification conditions becomes acidic in anode and becomes alkaline in cathode when voltage is applied. In addition, since anions such as chloride ions are pulled close to the anode, metal hydroxides having anion exchange activity can accommodate halogen ions, especially chlorine ions, which are the causative substances of ion migration very efficiently, It can be considered that the generation can be suppressed over a long period of time.

When an ion adsorbent is added to the photo-curable thermosetting resin composition as described above, it is possible to trap halogen ions such as chloride ions generated by heat or moisture, thereby removing impurity ions that adversely affect electrical insulation, Can be improved. Such an ion adsorbent is an ion getter having excellent ion exchange properties and heat resistance. It captures ionic impurities present in the system to control various problems caused by ions, It is used by adding to FPC adhesives, etc., and helps improve the reliability of electronic materials.

The ion adsorbent may be used singly or in combination of two or more depending on the kind of ion impurities to be trapped. Ion adsorbents include IXE-100, IXE-200, IXE-300, IXE-700F, IXE-770D, IXE-800, IXE-6107, IXEPLAS-A1, IXEPLAS- B1, and the like. In the present invention, a metal hydroxide is preferably used as the ion adsorbent, and it is also preferable that bipolar ion exchange is possible. More preferably, a mixture of hydrotalcite and zirconium phosphate is used. The form thereof is preferably a particulate form, and the particle size of the fine particles is preferably 1 mu m or less, more preferably 0.5 mu m or less.

The blending amount of the ion adsorbent is preferably 0.01-30 parts by mass, more preferably 0.2-30 parts by mass, and even more preferably 0.5-20 parts by mass, based on 100 parts by mass of the photocurable thermosetting resin composition. If the compounding amount of the ion adsorbent is more than the above range, the viscosity of the composition becomes too high and the rickleness of the composition becomes too high to lower the printability or adherence, which is undesirable. Conversely, if too small, the ion migration inhibiting effect becomes insignificant not.

(7) Core shell  At least one elastomer selected from a particulate elastomer and a silicone elastomer

The photo-curable thermosetting resin composition of the present invention comprises at least one elastomer selected from a core shell particle type elastomer and a silicone elastomer in order to improve the flexibility of the coating film without inhibiting the degree of curing such as glass transition temperature and hardness. A polybutadiene-modified epoxy resin or CTBN (CARBOXYL TERMINATED BUTADIENE ACRYLONITRILE) which is an inert elastomer is not preferable because it lowers the degree of curing such as a glass transition temperature.

The core of the core shell particle type elastomer is preferably selected from polybutadiene, silicone, SBR (styrene butadiene rubber), and a mixture thereof. As the shell, a polymer compatible with the core may be used. , A bisphenol A epoxy resin, and a bisphenol F epoxy resin.

Examples of the core shell particle type elastomer include MX-153, MX-257, MX-960, MX-170, MX-136, MX-965, MX-217, MX-416 and MX-551 of KANEKA have. These core shell granular elastomer products may be used alone or in combination of two or more.

As the silicone elastomer, a fine particle type epoxy functional silicone elastomer having a particle diameter of 1 탆 to 10 탆 may preferably be used. Examples of such silicone elastomer products include EP-5500, EP-5518, EP-2600, EP-2601 and EP-2720 from Dow Corning Toray. These fine particle type silicone elastomer products may be used alone or in combination of two or more.

The core-shell particle type elastomer or silicone elastomer is preferably dispersed in an epoxy resin at a high concentration. Examples of the epoxy resin used for dispersing these elastomers include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak type epoxy resin, glycidyl amino type epoxy resin, and alicyclic epoxy resin, or a combination of two or more thereof have. The content of the dispersed elastomer is preferably 10-40 parts by mass, more preferably 20-40 parts by mass, per 100 parts by mass of the epoxy resin. If the content of the dispersed elastomer is less than 10 parts by mass based on 100 parts by mass of the epoxy resin, the flexibility of the cured coating can not be improved. If the content of the dispersed elastomer is more than 40 parts by mass, dispersion characteristics are not obtained and exist as a foreign matter in the cured coating, (Core-shell granular elastomer), the development margin may be reduced, resulting in defects in the PCB working process (silicone elastomer).

The blending amount of the core shell particle type elastomer or silicone elastomer is preferably 1 to 20% by weight, and more preferably 5 to 15% by weight, based on the total weight of the composition. If the blending amount of the elastomer is less than 1 wt% of the total weight of the composition, the flexibility of the cured coating is insufficient, which is not preferable due to defects such as damage of the coating film due to impact or the like. The appearance of defective appearance due to the elastomer causes the tacky of the coating surface after the drying process due to the applied epoxy resin (core-shell particle type elastomer), and the developing margin may be reduced, resulting in defects in the PCB working process (Silicone elastomer) is not preferred.

(8) Colorant

The photo-curable thermosetting resin composition of the present invention may preferably further contain a colorant in addition to the above components. As such a coloring agent, pigments, dyes, pigments, coloring agents, and the like can be used. From the viewpoint of environmental load reduction and human influence, it is preferable that no halogen is contained.

Examples of the yellow colorant that can be used in the present invention include azo pigments, disazo pigments, condensed azo pigments, benzoimidazole pigments, isoindolinone pigments, and anthraquinone pigments, and specific examples thereof are as follows:

Pigment Yellow 001, 002, 003, 004, 005, 006, 009, 010, 012, 061, 062, 065, 073, 074, 075, 097, 100, 104, 105, 111, 116, 167, 169

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

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

Benzimidazole-based Pigment Yellow 120, 151, 154, 156, 175, 181

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

Anthraquinone-based Solvent Yellow 163, Pigment Yellow 024, 108, 147, 193, 199, 222

Examples of the blue colorant usable in the present invention include phthalocyanine-based, anthraquinone-based, and the like. 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 addition to the above, metal substituted or unsubstituted phthalocyanine compounds may be used.

The amount of the colorant to be added is not particularly limited, but is preferably 10 parts by mass or less, more preferably 0.1-5.0 parts by mass based on 100 parts by mass of the high heat-resistant resin containing the unsaturated double bond and the carboxyl group (1) .

The photo-curable thermosetting resin composition of the present invention may further contain components (for example, antifoaming agents) which are usually used in the curable resin composition, if necessary, in addition to the above components. Further, an organic solvent may be further added to suitably adjust the viscosity upon application of the composition.

The method of using the photocurable thermosetting resin composition of the present invention is as follows. First, the composition is adjusted to a viscosity suitable for the coating method with an organic solvent, and then coated on the substrate by a dip coating method, a flow coating method, a roll coating method, a bar coating method, a screen printing method or a curtain coating method, The organic solvent contained in the composition is volatilized and dried at a temperature of -120 캜. Then, 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 exposed to an aqueous alkali solution (0.1-3.0% aqueous solution of sodium carbonate) Thereby forming a pattern. The composition of the present invention contains a thermosetting component. When heated at a temperature of 130-160 DEG C, the carboxyl group of the high heat-resistant resin containing the unsaturated double bond and the carboxyl group and the carboxyl group of the The thermosetting component reacts to form a cured coating film excellent in heat resistance, chemical resistance, moisture absorption resistance, adhesion, electrical characteristics and the like.

Examples of the above-mentioned substrate include printed wiring boards or flexible printed wiring boards 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, A film, a PET film, a glass substrate, a ceramic substrate, a wafer substrate, or the like.

The volatile drying of the solvent after the application of the photocurable thermosetting resin composition of the present invention can be carried out by using a hot air circulating drying furnace, an infrared drying furnace, a hot plate, or the like.

After the photocurable thermosetting resin composition of the present invention is applied and volatilized and dried, the resulting coating film is exposed to active energy. The coating film is cured by exposure to active energy. 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 with a maximum wavelength of 340-420 nm, and both gas laser and solid state 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 photocurable 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 composition to a film such as polyethylene terephthalate and drying it, in addition to a method of directly applying the composition to a substrate in a liquid phase. Specific examples of using the photocurable thermosetting resin composition of the present invention as a dry film are as follows.

A dry film is a structure in which a base film, a solder resist layer, and a peelable cover film to be used, if necessary, are laminated in this order. The solder resist layer is a layer obtained by applying a developable photocurable 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 1-200 탆 is used. The solder resist layer is formed by uniformly applying a photo-curable 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 in a thickness range of 5-200 占 퐉 and drying. When a protective film is formed on a printed wiring board by using a dry film, the cover film is peeled off, the substrate on which the circuit is formed is overlapped with the solder resist layer, and the substrate is laminated with a laminator to form a solder resist layer . 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 may be peeled off either before exposure or after exposure.

Therefore, according to other aspects of the present invention, there is provided a solder resist obtained by applying and drying the photo-curable thermosetting resin composition, a solder resist dry film obtained by applying the photo-curable thermosetting resin composition to a substrate film and drying the solder resist film, There is provided a printed wiring board comprising a patterned cured product of a resin composition and a patterned cured layer of the above-mentioned photo-curable thermosetting resin composition.

2. Photocurable  Method for producing thermosetting resin composition

The photocurable thermosetting resin composition of the present invention can be produced by a conventional method. For example, the raw material components may be added to a reactor equipped with a stirrer, stirred and mixed, and then dispersed by a 3 roll mill. At this time, the raw material components may be all supplied simultaneously or sequentially. According to one embodiment of the present invention, the components other than the elastomer and the filler are first agitated and mixed at a low speed (for example, 500 rpm), and then an elastomer and a filler are further added thereto and stirred at a high speed (for example, 700 rpm) After completion of the stirring, the mixture is dispersed in a three-roll mill. Thereafter, when the dispersion is completed, the level of the particle size is confirmed, and when the particle size is 10 μm or more, dispersion is repeated.

Preferably, (1) wet-mixing a primary raw material mixture containing an unsaturated double bond and a high heat-resistant resin containing a carboxyl group, a thermosetting component and a filler together with an organic solvent in a mixer; (2) dispersing and mixing the wet mixture obtained in the step (1) using a bead mill; And (3) introducing a second raw material mixture containing a photopolymerization initiator into the dispersion mixture obtained in the step (2) and stirring and mixing the mixture. The photocurable thermosetting resin composition of the present invention can be produced by the method.

In the method for producing a photocurable thermosetting resin composition, optional components such as a reactive diluent, an ion adsorbent, an elastomer, and a coloring agent such as a pigment may be included in the first raw material mixture, the second raw material mixture, or both, It is included in the primary raw material mixture. According to a preferred embodiment of the present invention, all of the raw material components other than the photopolymerization initiator may be included in the first raw material mixture.

The bead mill dispersing device usable in the method for manufacturing a photocurable thermosetting resin composition is such that an inner container is rotatably coupled to an outer container so that a mixture in which the filler is wetted between the outer container and the inner container is dispersed while being rotated by the inner container . In this process, the pellets in the form of granules are dispersed in a uniform size.

The wet mixing of the filler using the mixer (for example, a homomixer) in the step (1) is preferably 20 minutes or more (for example, 20 minutes to 4 hours). If the wet mixing time is shorter than 20 minutes, the particles may not be uniform and large particles may remain. The viscosity of the wet mixture obtained in the step (1) is preferably less than 10,000 cPs (10 rpm, @ 25 ° C). If the viscosity of the wet mixture is higher than this range, it may be difficult to smoothly circulate the mixture in the bead mill dispersing device in the subsequent step (2), so that the filler may not be dispersed, Which is undesirable.

The beads used in the step (2) for dispersing the bead mill are preferably zirconia beads having a particle diameter of 0.5 mm to 2 mm, preferably about 1 mm. In the step (2), the rotation speed of the rotor during the dispersion of the bead mill is preferably from 5 to 400 rpm to 1600 rpm, more preferably from 10 to 800 rpm. If the rotational speed of the rotor is less than 5 Hz, there may be a problem that the particles are not dispersed and the particles remain intact. If the rotor speed exceeds 20 Hz, the resin properties may change due to temperature rise due to bead friction even if the filler is dispersed. The bead mill dispersion time is preferably 20 minutes to 2 hours, more preferably 50 minutes to 80 minutes. If the dispersing time of the bead mill is less than 20 minutes, there may be a problem that the particles are not dispersed and the particles remain intact. If the bead mill dispersion time exceeds 2 hours, there is a problem that the solvent volatilization and resin properties are changed and the productivity is lowered.

The mixing in the step (3) is preferably performed for 20 minutes or more (for example, 20 minutes to 3 hours). If the stirring time is shorter than this, the photoinitiator will not sufficiently dissolve in the resin, and the additive function will be degraded because the additive is not uniformly mixed with the dispersing raw material. If the agitation time is too long, the productivity decreases. The final photosensitive resin composition obtained after the step (3) preferably has a viscosity in the range of 20,000-25,000 cPs (10 rpm, @ 25 DEG C).

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 thereto.

[ Example ]

Example  One

(SR90-B3T4, solid content = 65%, acid value = 57 mgKOH / g, KCC) containing an unsaturated double bond and a carboxyl group and a thermosetting component (YD-012, bisphenol A Epoxy resin, softening point = 80 占 폚, equivalent = 650, Kukdo Chemical Co., Ltd.), and the mixture was stirred at 500 rpm for 10 minutes. After stirring, 10 g of a reactive diluent containing an unsaturated double bond (dipentaerythritol hexaacrylate (DPHA), Japanese explosive) and 30 g of a photopolymerization initiator (Irgacure 369, oxime ester photopolymerization initiator, BASF) were added sequentially and then a yellow colorant 6 g of a blue colorant (Pigment Blue 16:00, BASF), and 5 g of an ion adsorbent (IXEPLAS, a mixture of hydrotalcite and zirconium phosphate, Toa Gosei), and the mixture was stirred at 500 rpm for 10 minutes . After completion of the stirring, 100 g of core shell particle type elastomer (MX-170, core: silicone, core content: 25%, dispersion medium: bisphenol A epoxy resin, KANEKA) was added and stirred at 500 rpm for 10 minutes, -30, barium sulfate surface-treated, D (50) = 0.3 탆, SAKAI) was added three to six times. After completion of the addition, the mixture was stirred at 700 rpm for 20 minutes. At this time, the internal temperature was prevented from exceeding 45 ° C due to the heat generated by the high-speed agitation. After completion of stirring, the mixture was dispersed with a 3 roll mill. When the dispersion was completed, the level of the particle size was checked. When the particle size was 10 μm or more, dispersion was repeated. The prepared photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 13000 mPa · s.

Example  2

Except that 50 g of the core shell particle type elastomer (MX-170, core: silicone, core content: 25%, dispersion medium: bisphenol A epoxy resin, KANEKA) was used as the elastomer in Example 1, A composition was prepared. The prepared photocurable thermosetting resin composition had a solid content of 73% and a viscosity of 12500 mPa · s.

Example  3

Except that 100 g of the core shell particle type elastomer (MX-136, core: polybutadiene, core content: 25%, dispersion medium: bisphenol F epoxy resin, KANEKA) was used as the elastomer in Example 1, To prepare a resin composition. The prepared photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 12500 mPa · s.

Example  4

A photocurable thermosetting resin composition was prepared in the same manner as in Example 1, except that 100 g of a silicone elastomer (EP-2600, Dow Cornig Toray) was used as the elastomer. The prepared photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 13000 mPa · s.

Example  5

A photocurable thermosetting resin composition was prepared in the same manner as in Example 1, except that 50 g of a silicone elastomer (EP-2600, Dow Cornig Toray) was used as the elastomer. The prepared photocurable thermosetting resin composition had a solid content of 73% and a viscosity of 12500 mPa · s.

Example  6

A photocurable thermosetting resin composition was prepared in the same manner as in Example 1, except that 100 g of a silicone elastomer (EP-2601, Epoxy Functional, Dow Corning Toray) was used as the elastomer. The prepared photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 12500 mPa · s.

Comparative Example  One

A photocurable thermosetting resin composition was prepared in the same manner as in Example 1, except that the elastomer was not used. The prepared photocurable thermosetting resin composition had a solid content of 74% and a viscosity of 15000 mPa · s.

Comparative Example  2

A photocurable thermosetting resin composition was prepared in the same manner as in Example 1 except that 50 g of epoxidized polybutadiene (EPOLEAD PB-3600, molecular weight: 5900, acid value: 1 or less, DAICEL) was used as the elastomer. The prepared photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 13,500 mPa · s.

Comparative Example  3

A photocurable thermosetting resin composition was prepared in the same manner as in Example 1 except that 50 g of butadiene acrylonitrile (CTBN 1300X8, acrylonitrile content: 17%, CVC) was used as the elastomer. The prepared photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 13,500 mPa · s.

The glass transition temperature and modulus of the photocurable thermosetting resin compositions prepared in the Examples and Comparative Examples were measured using DMA (DYNAMIC MECHANICAL ANALYSIS) based on the standard JPCA standard. The dispersion degree of the produced photo-curable thermosetting resin composition was evaluated by a grindmeter and found to be 10 占 퐉 or less. Table 1 shows the compositions of the examples and comparative compositions, and the glass transition temperature and modulus measurement results.

As can be seen from the results of Table 1, Comparative Example 1, in which the elastomer was not applied, compared to Example 1-3, which is a composition using the core shell particle type elastomer, and Example 4-6, The temperature was equal but the modulus was significantly higher. When the modulus is high, the coating film is broken, resulting in defects such as film damage during the manufacturing process. In Comparative Examples 2 and 3 in which general elastomers were applied, the modulus was the same as in Examples but the glass transition temperature was about 10 캜 lower. This low glass transition temperature hinders the cure and leads to poor reliability.

On the other hand, the properties of the examples and comparative compositions were evaluated as follows.

After the circuit pattern substrate was subjected to a surface treatment, washing and drying, the photocurable thermosetting resin compositions of Examples and Comparative Examples were dried by a screen printing method and coated on the entire surface of the substrate to a thickness of about 25 μm. Lt; / RTI > for 30 minutes. For the exposure process after drying, an exposure apparatus equipped with a high-pressure mercury lamp was used as the exposure apparatus, and a 41-step tablet (manufactured by HITACHI CHEMICAL) was used for sensitivity evaluation. The exposure process was carried out using this apparatus, and the resist film was developed with a 1% aqueous solution of sodium carbonate at 30 DEG C for 90 seconds. Optimum exposure conditions were selected through the sensitivity results (sensitivity = 6 stages) of the step tablet.

Evaluation of developing margin

The composition was applied on a substrate by screen printing, dried at 80 占 폚, taken out at intervals of 10 minutes from 30 minutes to 100 minutes, and then cooled at room temperature. Thereafter, the maximum allowable drying time at which the residue did not remain during development for 90 seconds in a 1% sodium carbonate aqueous solution at 30 캜 was defined as a developing margin.

TACKY  evaluation

The composition was applied onto the substrate by screen printing, dried at 80 DEG C for 30 minutes, and then cooled at room temperature. When a pattern mask film made of a polyester material was pressed on this substrate for 1 minute and the pattern mask film was peeled off, the film was evaluated for TACKY on the basis of 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

Resolution

The composition was applied onto the substrate by screen printing, dried at 80 DEG C for 30 minutes, and then cooled at room temperature. The pattern mask film was pressed on this substrate and exposed at 600 mJ / cm ² through an exposure device equipped with a high-pressure mercury lamp, and developed with a 1% sodium carbonate aqueous 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.

Solder heat resistance

The composition was applied onto the substrate by screen printing, dried at 80 DEG C for 30 minutes, and then cooled at room temperature. After exposure of this substrate to 600mJ / cm ² through an exposure machine with a high pressure mercury lamp was exposed to the 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 캜 for 10 seconds. The immersion step was repeated three times. At this time, the external appearance of the solder resist layer and whether or not the solder resist layer was peeled off were visually evaluated based on the following criteria.

○: none of the external changes and exfoliation

DELTA: Fine appearance change and fine peeling

X: Excessive contour change and film peeling

Flexibility

The composition was applied onto the substrate by screen printing, dried at 80 DEG C for 30 minutes, and then cooled at room temperature. After exposure of this substrate to 600mJ / cm ² through an exposure machine with a high pressure mercury lamp was exposed to the further 1100mJ / cm ^2. Thereafter, the mixture was heated at 150 DEG C for 60 minutes to complete the final curing. The substrate thus obtained was folded at an angle of 90 [deg.] And the unfolding was repeated three times. At this time, the external appearance of the solder resist layer and whether or not the solder resist layer was peeled off were visually evaluated based on the following criteria.

○: none of the external changes and exfoliation

DELTA: Fine appearance change and fine peeling

X: Excessive contour change and film peeling

PCT

The substrate produced through the above process was treated under 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) Were evaluated according to the following criteria.

○: No change in appearance, discoloration or dissolution

DELTA: Subtle appearance change, some discoloration, and elution

X: severe appearance change, excessive discoloration and elution

HAST

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. This substrate was subjected to a HAST evaluation for 168 hours under a high-temperature and high-humidity condition of a temperature of 130 캜 and a humidity of 85%, and a voltage of 5 V was applied. After 168 hours, the insulation resistance was evaluated according to the following criteria.

○: 108 Ω or more

?: 106 to 108?

X: Not more than 106 Ω

The evaluation results of the characteristics are shown in Table 2 below.

Dry Film Production and Evaluation

Each of the photo-curable thermosetting compositions of Examples and Comparative Examples was 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 600mJ / cm ² after the exposure system through a high-pressure mercury lamp is mounted as shown in the step 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 above-mentioned characteristics were evaluated for the substrate thus obtained, and the results are shown in Table 3 below.

As can be seen from the results of Tables 2 and 3, the use of an elastomer which does not inhibit the curing degree, such as glass transition temperature, of the photocurable thermosetting resin composition of the present invention improved PCT resistance, HAST resistance and flexibility, Reliability such as resistance and HAST resistance, and defects such as film damage during the manufacturing process can be improved. That is, the photocurable thermosetting resin composition of the present invention combines the flexibility required for PCT resistance, heat resistance and HAST resistance, which are indispensably required for solder resists for semiconductor packages, and is very suitable for solder resists and solder resists for thin film packages Suitable.

On the other hand, the following processes were performed to compare the productivity of the resin composition manufacturing method using the bead mill and the manufacturing method using the three roll mill.

Bead mill  Process sequence and time

(1) Primary raw material mixture (high heat-resistant resin, thermosetting component, filler and solvent) Input and wet mixing: 4 hours

(2) Bead mill dispersion: 2 hours

(3) Secondary raw material mixture (all of the remaining raw material ingredients) Addition and stirring Mixing: 3 hours

(4) Calibration solvent Mix after addition: 1 hour

- Total manufacturing time (based on 400kg): 10 hours

- Final yield: 85%

- Productivity per hour: 34.0 kg / hr

3 Roll mill process sequence and time required

(1) All ingredients and wet mixing: 4 hours

(2) 3-roll mill dispersion (2 passes, 1 pass = 400 kg / 4 hours): 8 hours

(3) Calibration solvent Mixing after addition: 1 hour

- Total manufacturing time (based on 400kg): 13 hours

- Final yield: 85%

- Productivity per hour: 26.1 kg / hr

Further, the photo-curable thermosetting resin compositions each prepared by a method using a bead mill and a method using a three-roll mill were evaluated for developing margin, sensitivity, resolution, tacky resistance, solder heat resistance and PCT characteristics in the same manner as described above , And the results are shown in Table 4 below.

As can be seen from the results of Table 4, when the photosensitive resin composition of the present invention is prepared by a method using a bead mill, it is possible to obtain a composition similar in characteristics to the composition prepared by the method using the three roll mill, And the productivity was remarkably improved.

Claims (17)

(1) a high heat-resistant resin containing an unsaturated double bond and a carboxyl group,
(2) a photopolymerization initiator,
(3) a reactive diluent containing an unsaturated double bond,
(4) a thermosetting component,
(5) fillers,
(6) an ion adsorbent and
(7) Core shell One or more elastomers selected from a particulate elastomer and a silicone elastomer
Wherein the thermosetting resin composition is a thermosetting resin composition. The thermosetting thermosetting resin composition according to Claim 1, wherein the unsaturated double bond of the high heat-resistant resin containing an unsaturated double bond and a carboxyl group is derived from acrylic acid or methacrylic acid or a derivative thereof and the carboxyl group is derived from a polybasic acid anhydride Composition. The photocurable thermosetting resin composition according to claim 1, wherein the photopolymerization initiator is at least one selected from an oxime ester photopolymerization initiator, an? -Acetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. The photo-curable thermosetting resin composition according to claim 1, wherein the reactive diluent containing the unsaturated double bond contains 2-6 unsaturated double bonds. The photocurable thermosetting resin composition according to claim 1, wherein the thermosetting component is a compound having two or more cyclic ether groups or thioether groups in the molecule. The photocurable thermosetting resin composition according to claim 1, wherein the ion adsorbent is a mixture of hydrotalcite and zirconium phosphate. The photocurable thermosetting resin composition according to claim 1, wherein the core of the core shell particle type elastomer is selected from polybutadiene, silicone, styrene butadiene rubber, and mixtures thereof, and the shell is an epoxy resin. The photocurable thermosetting resin composition according to claim 1, wherein the silicone elastomer is a fine particle type epoxy functional silicone elastomer having a particle diameter of 1 탆 to 10 탆. The photocurable thermosetting resin composition according to claim 1, further comprising a colorant. A solder resist obtained by applying and drying the photocurable thermosetting resin composition according to any one of claims 1 to 9. A solder resist dry film obtained by applying the photocurable thermosetting resin composition according to any one of claims 1 to 9 to a base film and drying the base film. A patterned cured product of the photocurable thermosetting resin composition according to any one of claims 1 to 9. A printed wiring board comprising a patterned cured layer of the photocurable thermosetting resin composition according to any one of claims 1 to 9. 10. A method of producing a photocurable thermosetting resin composition according to any one of claims 1 to 9,
(1) wet-mixing a primary raw material mixture containing an unsaturated double bond and a high heat-resistant resin containing a carboxyl group, a thermosetting component and a filler together with an organic solvent in a mixer;
(2) dispersing and mixing the wet mixture obtained in the step (1) using a bead mill; And
(3) adding a secondary raw material mixture containing a photopolymerization initiator to the dispersion mixture obtained in the step (2) and stirring and mixing. 15. The method of claim 14, wherein the wet mixing of step (1) is performed for 20 minutes or more. 15. The method according to claim 14, wherein the bead mill dispersion of step (2) is performed for 20 minutes to 2 hours. 15. The method according to claim 14, wherein the stirring mixture of step (3) is performed for 20 minutes or more.