KR101732986B1

KR101732986B1 - Photosensitive resin composition with good reliability and heat resistance and printed circuit board using the same

Info

Publication number: KR101732986B1
Application number: KR1020150041505A
Authority: KR
Inventors: 이민성; 김영진; 단철호; 서호연
Original assignee: 주식회사 케이씨씨
Priority date: 2015-03-25
Filing date: 2015-03-25
Publication date: 2017-05-08
Also published as: KR20160114960A

Abstract

The present invention relates to a photosensitive resin composition excellent in heat resistance and reliability and a printed circuit board using the same. More particularly, the present invention relates to a solder resist for a semiconductor package, which is excellent in PCT resistance, HAST resistance, electroless gold plating resistance, To a printed circuit board in which a cured film having excellent heat resistance and reliability can be formed, a dry film and a cured product thereof, and a cured film such as a solder resist formed thereon.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition which is excellent in heat resistance and reliability and a printed circuit board using the same. BACKGROUND ART [0002]

At present, some liquid developer solder resists are used in solder resists of some commercial printed wiring boards and most industrial printed wiring boards, forming patterns by ultraviolet irradiation after development from high precision and high density, and finally curing by irradiation with heat and / or light have. However, from the viewpoint of environmental considerations, alkali developing type photo-solder resists using an alkaline aqueous solution as a developer have become mainstream, and they are used in large quantities in the production of actual printed wiring boards.

In addition, in recent years, in response to the increase in the density of printed wiring boards due to the thinning and shortening of electric / electronic devices, workability and high performance are required for solder resist. However, current alkaline developing type photo-solder resists still have a problem in terms of durability. That is, alkaline resistance, water resistance and heat resistance are lower than those of conventional thermosetting and solvent-developing type solder resists. This is because alkali-developing type photo-solder resists must have a hydrophilic group as a main component in order to enable alkaline development. As a result, penetration of water, water vapor or the like is easy and the chemical resistance is lowered or the adhesiveness between the resist film and copper is lowered . As a result, alkali resistance is poor. Especially in semiconductor packages such as ball grid array (BGA) and chip scale package (CSP), resistance to PCT (pressure cooker tester) It is reality that we do not have outside. In addition, in the HAST (Highly Accelerated Stress Test) test under the condition of applying the voltage under the humidifying condition, the migration is confirmed to have occurred in most cases within several hours.

Recently, the transition to the surface mounting tends to increase the temperature of the package to a very high level, such as the use of the lead-free solder in consideration of the environmental problem. As a result, the reaching temperature inside / outside the package becomes remarkably high, In the photosensitive resist, there is a problem that cracks are generated in the film due to thermal shock or peeled off from the substrate or EMC, and improvement thereof is required. In addition, since the hardened film becomes thinner as the thinned and shortened film is thinned, a hardened film excellent in heat resistance is further required to improve reliability.

As the carboxyl group-containing resin used in conventional solder resists, an epoxy acrylate-modified resin derived from the modification of an epoxy resin is generally used. For example, Japanese Unexamined Patent Publication (Kokai) No. 61-243869 discloses a solder resist composition comprising a photosensitive resin, a photoinitiator, a diluent, and an epoxy compound to which an acid anhydride is added to the reaction product of a novolak type epoxy compound and an unsaturated monobasic acid have. Japanese Unexamined Patent Publication (Kokai) No. Hei 3-250012 discloses that (meth) acrylic acid is added to an epoxy resin obtained by reacting epichlorohydrin with the reaction product of salicylic aldehyde and monovalent phenol, and additionally a polybasic carboxylic acid or There is disclosed a solder resist composition comprising a photosensitive resin obtained by reacting an anhydride, a photoinitiator, an organic solvent and the like.

A general solder resist composition including an acid modified epoxy acrylate, a photoinitiator, a reactive diluent, a thermosetting component and the like has almost no problem in reliability in a conventional package. However, in the case of a thin package, the heat resistance of the cured coating is insufficient, And deformation of the film due to expansion in the manufacturing process may be caused. Therefore, it is a fact that the cured coating having poor heat resistance shows a limit of reliability when applied to a thin-walled package.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in an effort to solve the above problems of the prior art, and it is an object of the present invention to provide a cured film having a high glass transition temperature and securing excellent heat resistance while securing PCT resistance, HAST resistance, electroless gold plating resistance, There is provided a printed wiring board comprising a photo-curable thermosetting resin composition suitable for a solder resist requiring high reliability and a solder resist for a thin film package having a very thin thickness, a dry film thereof and a cured product thereof, and a cured film such as a solder resist formed thereon It is a technical task.

In order to achieve the above technical object, the present invention provides a thermosetting resin composition comprising (1) a high heat resistant resin containing an unsaturated double bond and a carboxyl group, (2) a photopolymerization initiator, (3) a thermosetting component, (4) filler, Wherein the reactive diluent component is a combination of at least one reactive diluent containing an aliphatic group and an unsaturated double bond and at least one reactive diluent containing an aromatic ring group and an unsaturated double bond.

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.

The photo-curable thermosetting resin composition according to the present invention is excellent in PCT resistance, HAST resistance, electroless gold plating resistance and thermal shock resistance as a solder resist for a semiconductor package, and has an excellent glass transition temperature to form an excellent cured film exhibiting excellent heat resistance And can be suitably used for a solder resist requiring a high reliability and a solder resist for a thin film package having a very thin thickness.

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

The photocurable 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 thermosetting component, (4) filler and Wherein the reactive diluent component is a combination of at least one reactive diluent containing an aliphatic group and an unsaturated double bond and at least one reactive diluent containing an aromatic ring group and an unsaturated double bond.

(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 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 group having 2-20 carbon atoms, or a benzoyl group; 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) 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.

(4) 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.

(5) Reactive diluent

The reactive diluent component 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 alkali 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 reactive diluent compounds may contain, for example, from 1 to 6 unsaturated double bonds in the skeleton and may exhibit differences in the flexibility and strength of the cured coating film and the reliability of the composition depending on the number of unsaturated double bonds.

In the present invention, in order to increase the glass transition temperature of the cured coating and ensure excellent heat resistance, at least one reactive diluent containing an aliphatic group and an unsaturated double bond as a reactive diluent component and at least one reactive diluent containing an aromatic ring group and an unsaturated double bond Use a combination.

Use of only a reactive diluent containing an aliphatic group and an unsaturated double bond results in a thicker cured film because the glass transition temperature of the cured film is lowered, which is not desirable for a thin thickness package. On the other hand, when only a reactive diluent containing an aromatic ring group and an unsaturated double bond is used, the glass transition temperature is increased, but the composition separation is increased, and compatibility with other components is poor, resulting in poor appearance of the cured coating.

Because of the aromatic ring, the cured coating is preferable because it can ensure a high glass transition temperature and exhibit excellent heat resistance.

For reference, the structures of a reactive diluent containing an aliphatic group and an unsaturated double bond, and a reactive diluent containing an aromatic ring group and an unsaturated double bond can be briefly shown as the following schematic diagrams (6) and (7), respectively.

Specific examples of the reactive diluent containing an aliphatic group and an unsaturated double bond include caprolactone acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dimethylpropane tetraacrylate, trimethyl Propylene triacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, dipentaerythritol caprolactone acrylate, and combinations thereof. Products of reactive diluents containing aliphatic groups and unsaturated double bonds include DPHA, DPCA-30; Miramer M200, Miramer M300, and Miramer M600.

Specific examples of the reactive diluent containing an aromatic ring group and an unsaturated double bond include a reactive diluent derived from an aromatic compound selected from a bisphenol A compound, a bisphenol F compound, a phenol novolak compound, a cresol novolak compound, A compound containing an aromatic ring group and an unsaturated double bond. Examples of products of reactive diluents containing aromatic ring groups and unsaturated double bonds include products having an aromatic ring of bisphenol of Cytec (ebecryl-600, ebecryl-604, ebecryl-605, ebecryl-606, ebecryl-607, ebecryl- ebecryl-609, ebecryl-645, ebecryl-648, ebecryl-1608, ebecryl-2958, ebecryl-3105, ebecryl-3200, ebecryl-3500, ebecryl- 3720, ebecryl-9686, ebecryl-9740, etc.); (Ebecryl-629, ebecryl-639, ebecryl-3603, ebecryl-9626, ebecryl-9636, ebecryl-9656, ebecryl-9695, ebecryl-9706, ebecryl-9716, etc.) having a novolak-type aromatic ring of Cytec; (Miramer Pe-110, Miramer Pe-220, Miramer Pe-230, Miramer Pe-2310, Miramer Pe-240, Miramer Pe-310, Miramer Ea-2235, Miramer Ea-2255) having an aromatic ring of bisphenol , Miramer Ea-2259, Miramer Ea-2280, Miramer Me-2010, Miramer Me-2100, etc.); (Miramer Epr-400, Miramer Sc 6400, etc.) having a Novolac-type aromatic ring of Miwon.

The reactive diluent containing an aromatic ring group and an unsaturated double bond may be diluted with components such as TPGDA (Tripropylene glycol diacrylate), TPGTA (Tripropylene glycol Triacrylate) and TMPTA (Trimethylopropane Triacrylate). If diluted with the above components, the flexibility, strength, and reliability of the cured coating may differ depending on the functional groups of the diluent.

The content of the reactive diluent containing an aromatic ring group and an unsaturated double bond is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, per 100 parts by mass of the reactive diluent. When the content of the aromatic cyclic reactive diluent is less than 10 parts by mass in the total 100 parts by mass of the reactive diluent, the heat resistance of the cured coating may not be sufficient. When the amount exceeds 90 parts by mass, the polarity is increased due to excessive aromatic ring components, Resulting in poor appearance of the coating film.

In the photocurable thermosetting resin composition of the present invention, the total amount of the reactive diluent component is preferably 5 to 90 parts by mass, more preferably 10 to 70 parts by mass, per 100 parts by mass of the high heat resistant resin containing the unsaturated double bond and the carboxyl group, The mass addition is more preferred. If the blending amount of the total reactive diluent is less than 5 parts by mass based on 100 parts by mass of the high heat resistant resin (1), photo-curability deteriorates and pattern formation becomes difficult due to the development of an aqueous alkaline solution after irradiation of active energy, While if it exceeds 90 parts by mass, the solubility in an aqueous alkali solution is lowered.

(6) 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, and more preferably 0.1-5 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 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 coating 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.

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, 7 g of a reactive diluent (M600, dipentaerythritol hexaacrylate, Miwon Chemical Co.) containing an aliphatic group and an unsaturated double bond and a reactive diluent (ebecryl-2958, bisphenol A type, Cytec) containing an aromatic ring group and an unsaturated double bond, (Pigment Yellow 147, BASF) and 6 g of a blue colorant (Pigment Blue 16: 00, BASF) were sequentially added, and the mixture was stirred at room temperature for 3 hours. The mixture was stirred at 500 rpm for 10 minutes. After completion of the stirring, 250 g of a filler (B-30, surface treated barium sulfate, D (50) = 0.3 탆, SAKAI) was added three to six times, and 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 74% and a viscosity of 13800 mPa · s.

Example 2

5 g of a reactive diluent containing an aliphatic group and an unsaturated double bond (M600, dipentaerythritol hexaacrylate, Miwon Chemical Co., Ltd.) as a reactive diluent, a reactive diluent containing an aromatic ring group and an unsaturated double bond (ebecryl-2958, bisphenol A type, Cytec) was used instead of 5 g of the photocurable thermosetting resin composition. The prepared photocurable thermosetting resin composition had a solid content of 74% and a viscosity of 13100 mPa · s.

Example 3

7 g of a reactive diluent containing an aliphatic group and an unsaturated double bond (M600, dipentaerythritol hexaacrylate, Miwon Chemical Co., Ltd.) as a reactive diluent, a reactive diluent containing an aromatic ring group and an unsaturated double bond (ebecryl-9656, Cytec) was used instead of 3g of the photo-curable thermosetting resin composition. The obtained photocurable thermosetting resin composition had a solid content of 74% and a viscosity of 14100 mPa · s.

Example 4

5 g of a reactive diluent containing an aliphatic group and an unsaturated double bond (M600, dipentaerythritol hexaacrylate, Miwon Chemical Co., Ltd.) as a reactive diluent, a reactive diluent containing an aromatic ring group and an unsaturated double bond (ebecryl-9656, Cytec) was used instead of 5 g of the photocurable thermosetting resin composition. The prepared photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 13800 mPa · s.

Comparative Example One

A photocurable thermosetting resin composition was prepared in the same manner as in Example 1, except that 10 g of a reactive diluent (M600, dipentaerythritol hexaacrylate, Miwon Chemical Co., Ltd.) containing an aliphatic group and an unsaturated double bond was used as a reactive diluent component . The solid content of the prepared photocurable thermosetting resin composition was 74% and the viscosity was 13,000 mPa · s.

Comparative Example 2

A photocurable thermosetting resin composition was prepared in the same manner as in Example 1, except that 10 g of a reactive diluent (ebecryl-2958, bisphenol A type, Cytec) containing an aromatic ring group and an unsaturated double bond was used as a reactive diluent component. The obtained photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 14500 mPa · s.

Comparative Example 3

A photocurable thermosetting resin composition was prepared in the same manner as in Example 1, except that 10 g of a reactive diluent (ebecryl-9656, cresol noble-lock type, Cytec) containing an aromatic ring group and an unsaturated double bond was used as a reactive diluent component. The prepared photocurable thermosetting resin composition had a solid content of 74% and a viscosity of 14,800 mPa · s.

The silicone antifoaming agent (KS66, Shin-Etsu) and the solvent were added to each of the photocurable thermosetting resin compositions prepared in the above Examples and Comparative Examples and the glass transition temperature was measured using DMA (DYNAMIC MECHANICAL ANALYSIS) based on the standard JPCA standard Respectively. In addition, the compatibility of the charged raw materials in the produced photo-curable thermosetting resin composition was evaluated. 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 compatibility test results.

As can be seen from the results of Table 1, all of the compositions of the present invention satisfied excellent glass transition temperature and compatibility at the same time, whereas Comparative Example 1 was excellent in compatibility but had a low glass transition temperature and Comparative Examples 2 and 3 The glass transition temperature was high but the compatibility was poor.

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 the 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 the substrate and exposed at 600 mJ / cm ² through an exposing 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: Severe contour change and film peeling present

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.

○: More than 10 ⁸ Ω

Δ: 10 ⁶ to 10 ⁸ Ω

X: 10 ⁶ Ω or less

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 compositions of the present invention satisfied all of the evaluation items in both the liquid type and the dry film type, Resistance and HAST resistance were poor, and Comparative Examples 2 and 3 had poor flexibility in both liquid type and dry film types.

Claims

(1) a high heat-resistant resin containing an unsaturated double bond and a carboxyl group,
(2) a photopolymerization initiator,
(3) a thermosetting component,
(4) fillers and
(5) a reactive diluent component,
Wherein the reactive diluent component comprises at least one reactive diluent containing an aliphatic group and an unsaturated double bond; And at least one reactive diluent containing an aromatic ring group and an unsaturated double bond in a weight ratio of from 5: 5 to 7: 3.
A photocurable 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 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 method according to claim 1, wherein the reactive diluent containing an aliphatic group and an unsaturated double bond is selected from the group consisting of caprolactone acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dimethylpropane tetraacryl Acrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, dipentaerythritol caprolactone acrylate, and combinations thereof. A photocurable thermosetting resin composition.

The positive resist composition according to claim 1, wherein the reactive diluent containing the aromatic ring group and the unsaturated double bond is an aromatic compound selected from the group consisting of a bisphenol A compound, a bisphenol F compound, a phenol novolak compound, a cresol novolak compound, Wherein the photo-curable thermosetting resin composition is a compound containing an aromatic ring group derived from a compound and an unsaturated double bond.

The photocurable thermosetting resin composition according to claim 1, wherein the content of the reactive diluent containing the aromatic ring group and the unsaturated double bond is 10 to 90 parts by mass with respect to 100 parts by mass of the reactive diluent.

The photocurable thermosetting resin composition according to claim 1, further comprising a colorant.

A solder resist obtained by applying and drying the photo-curable thermosetting resin composition according to any one of claims 1 to 8.

A solder resist dry film obtained by applying the photocurable thermosetting resin composition according to any one of claims 1 to 8 to a base film and drying the same.

The patterned cured product of the photocurable thermosetting resin composition according to any one of claims 1 to 8.

A printed wiring board comprising a patterned cured layer of the photocurable thermosetting resin composition according to any one of claims 1 to 8.