WO2013125854A1 - Radiation curable and thermosettable resin composition, and dry film solder resist - Google Patents
Radiation curable and thermosettable resin composition, and dry film solder resist Download PDFInfo
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- WO2013125854A1 WO2013125854A1 PCT/KR2013/001339 KR2013001339W WO2013125854A1 WO 2013125854 A1 WO2013125854 A1 WO 2013125854A1 KR 2013001339 W KR2013001339 W KR 2013001339W WO 2013125854 A1 WO2013125854 A1 WO 2013125854A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Definitions
- Resin composition which has photocurability and thermosetting, and dry film soldering resist
- the present invention relates to a resin composition and a dry film solder resist (DFSR) which are photocurable and thermosetting. More specifically, the present invention relates to a resin composition and DFSR having a photocurable and thermosetting property capable of providing a DFSR having a lower coefficient of thermal expansion (CTE) and improved heat resistance.
- CTE coefficient of thermal expansion
- photosensitive solder resists capable of forming fine opening patterns are used for printed circuit boards, semiconductor package substrates, and flexible circuit boards.
- Semiconductor packaged products are composite materials consisting of epoxy molding, insulators such as solder resist, semiconductors such as chip dies, and conductors such as substrate circuit patterns. It should be cold. However, due to the difference in the coefficient of thermal expansion (CTE) of each of the insulators, semiconductors, and conductors, the dimensional instability and warpage of the component appear as a problem. This phenomenon causes a mismatch between the chip and the organ when connecting the chip die and the semiconductor substrate with solder balls or gold wires, and also causes the crack and fracture of the product due to shear forces, which may affect the life of the product. Can be. In recent years, as the thickness of the substrate becomes thinner, such dimensional stability and warpage have become more problematic. In order to solve this problem, materials are being developed to minimize CTE mismatch between materials, and solder resists are also required to be developed as solder resists having a lower coefficient of thermal expansion.
- CTE coefficient of thermal expansion
- the thermal expansion coefficient of the previously known dry film solder resist is 45 to 70 ppm of al (coefficient of thermal expansion before Tg) and 140 of a2 (coefficient of thermal expansion after Tg). To 170 ppm.
- the solder resist is required to have characteristics such as developability, high resolution, insulation, adhesion, soldering heat resistance, and gold plating resistance.
- characteristics such as developability, high resolution, insulation, adhesion, soldering heat resistance, and gold plating resistance.
- solder resists for semiconductor package substrates in addition to these properties, for example, the temperature resistance test (TCT) of -65 ° C. to 150 ° C., or crack resistance or HAST (Highly Accelerated) between fine wirings. Stress Test) characteristics are required.
- TCT temperature resistance test
- HAST Highly Accelerated
- solder resists Conventionally, resin compositions having photocurable and thermosetting properties, including photopolymerizable monomers such as polyfunctional acrylates, have been used together with acid-modified oligomers, photoinitiators and thermosetting binders to form solder resists.
- the solder resist formed from such a resin composition does not have a high glass transition temperature, and thus the heat resistance reliability is insufficient.
- the PCT resistance, TCT heat resistance, and HAST resistance between fine wirings required for the package substrate material of the semiconductor device are prevented. There was a disadvantage of not properly striking.
- the present invention provides a higher glass transition temperature and a lower coefficient of thermal expansion (CTE, It is to provide a resin composition having photocurability and thermosetting which can provide DFSR with improved thermal reliability along with Coefficient of Thermal Expansion.
- CTE coefficient of thermal expansion
- the present invention provides a DFSR having a lower coefficient of thermal expansion (CTE) and improved heat resistance.
- CTE coefficient of thermal expansion
- the present invention is an acid-modified oligomer comprising a carboxyl group (-C00H) and an iminocarbonate compound having a photocurable unsaturated functional group; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; And a photocurable and thermosetting resin composition comprising a photoinitiator.
- the resin composition When cured, the resin composition may have a coefficient of thermal expansion ( ⁇ ) of 10 to 35 ppm before the glass transition temperature (Tg), and may have a coefficient of thermal expansion ( ⁇ 2) of 150 ppm or less after the glass transition temperature ().
- the iminocarbonate-based compound may be formed by reacting 1) a cyanate ester compound, 2) a dicarboxylic acid compound, and 3) a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group.
- the dicarboxylic acid compound may be an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, or an aromatic dicarboxylic acid compound.
- the dicarboxylic acid compound and the compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group may be used in a molar ratio of 2: 8 to 8: 2 to react with the cyanate ester compound.
- the dicarboxylic acid compound is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, server acid, azelaic acid, sebacic acid, norbornene dicarboxylic acid, C5-C10 cycloalkane ( CYCL0ALKANE) dicarboxylic acids, acid anhydrides thereof, or combinations of two or more of these compounds.
- dicarboxylic acid compound examples include phthalic acid, norbornene dicarboxylic acid, Tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid, pyridine dicarboxylic acid, acid anhydrides thereof, or two of these compounds The above combination may be included.
- the compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group is acrylic acid, methacrylic acid, cinnamic acid, butenoic acid, hexenoic acid, 2-allylphenol, hydroxy Styrene, hydroxycyclonucleene, hydroxy naphthoquinone (5—hydroxy 1-p—naphthoquinone) or a combination of two or more thereof.
- the cyanate ester compound may include a bisphenol or novolac compound having a cyanide group (-0CN).
- the acid-modified oligomer may include an iminocarbonate-based compound of Formula 1 below.
- n is an integer of 1 to 100
- 3 ⁇ 4 is a functional group derived from a compound having a photocurable unsaturated functional group and a hydroxy group or a carboxy group
- R 2 is a functional group derived from a dicarboxylic acid compound.
- the acid-modified oligomer may be included in 15 to 75% by weight based on the total weight of the resin composition.
- the photopolymerizable monomer may include an acrylate compound having two or more photocurable unsaturated functional groups.
- the photopolymerizable monomer may be a hydroxyl group-containing acrylate compound, a water-soluble acrylate compound, a polyester acrylate compound, a polyurethane acrylate compound, an epoxy acrylate compound, a caprolactone modified acrylate compound, or two kinds thereof. The above combination may be included.
- the photopolymerizable monomer may be included in 5 to 30% by weight based on the total weight of the resin composition. .
- the photoinitiator is composed of benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, ⁇ -aminoacetophenones, acylphosphine oxides, and oxime esters. It may include one or more selected from the group.
- the photoinitiator may be included in 0.5 to 20% by weight based on the total weight of the resin composition.
- the thermosetting functional group may be at least one selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thio ether group.
- the thermosetting binder may be included in an amount of 0.8 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer.
- the resin composition which has the said photocurability and thermosetting property is a solvent; And thermosetting binder catalysts, fillers, pigments and additives
- the present invention is an acid-modified oligomer comprising a carboxyl group (-C00H) and an iminocarbonate compound having a photocurable unsaturated functional group;
- Photopolymerizable monomers having two or more photocurable unsaturated functional groups; And a cured product of a thermosetting binder having a thermosetting functional group.
- the cured product includes a crosslinked structure in which the carboxyl group of the iminocarbonate-based compound and the thermosetting functional group are crosslinked; A crosslinked structure in which the unsaturated functional groups of the iminocarbonate compound and the photopolymerizable monomer are crosslinked with each other; And a triazine crosslinked structure of Formula 2 derived from the iminocarbonate-based compound:
- Dry film solder resist provided from the resin composition according to the triazine cross-linked structure represented by the formula (2) is compared with the structure using an acid-modified epoxy acrylate based on the existing novolac structure (novolac) It can have a higher glass transition temperature (Tg) and a lower coefficient of thermal expansion, thereby exhibiting improved heat resistance reliability.
- the DFSR not only can satisfy various physical properties such as PCT resistance, TCT heat resistance, and HAST resistance between fine wirings required for the package substrate material of the semiconductor device, but also reduce warpage and reduce defects. It can extend the life of the product.
- the dry film solder resist may have a thermal expansion coefficient ( ⁇ ) of 10 to 35 ppm before the glass transition temperature (Tg), and may have a thermal expansion coefficient ( ⁇ 2) of 150 ppm or less after the glass transition temperature (Tg).
- the dry film solder resist may further include a photoinitiator dispersed in the cured product.
- the dry film solder resist may have a glass transition temperature (Tg) of 130 to 180 ° C.
- the dry film solder resist is a package substrate of a semiconductor device Can be used for manufacture.
- the resin composition of the present invention includes a specific acid-modified oligomer
- a predetermined triazine crosslinked structure can be formed in the hardened
- the resin composition may include a photopolymerizable monomer having two or more photocurable unsaturated functional groups, so that the final product, DFSR, may have higher glass transition temperature (Tg) and low thermal expansion coefficient as well as improved heat resistance reliability.
- a DFSR capable of exhibiting excellent physical properties such as excellent PCT resistance, TCT heat resistance, and HAST resistance between fine interconnects, and to reduce warpage. It can be used preferably for package substrate manufacture.
- an acid-modified oligomer including an carboxyl group (-C00H) and an iminocarbonate-based compound having a photocurable unsaturated functional group; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; And a photocurable and thermosetting resin composition comprising a photoinitiator.
- the resin composition includes an acid-modified oligomer, a photopolymerizable monomer, a photoinitiator, and a thermosetting binder.
- an iminocarbonate-based compound having a carboxyl group and a photocurable unsaturated functional group is included as an acid-modified oligomer.
- DFSR can be formed.
- exposure is selectively performed to the resin composition of the part in which DFSR is to be formed.
- acid-modified oligomers for example, unsaturated functional groups contained in the iminocarbonate-based compound, and unsaturated functional groups contained in the photopolymerizable monomer cause photocuring.
- Crosslinking can be formed with each other, and as a result, a crosslinked structure by photocuring in the exposed portion can be formed.
- the resin composition of the exposed part having the crosslinked structure is left on the substrate as it is, and the resin composition of the remaining non-exposed part may be dissolved in the developer and removed.
- the carboxyl group contained in the acid-modified oligomer for example, an iminocarbonate-based compound reacts with the thermosetting functional group of the thermosetting binder to crosslink.
- a bond can be formed, and as a result, a DFSR can be formed in a desired portion on the substrate while forming a crosslinked structure by thermal curing.
- the resin composition includes the imino carbonate-based compound as an acid-modified oligomer
- a secondary crosslinked structure in the thermosetting process for example, a triazine crosslinked structure represented by Chemical Formula 2, etc. Can be formed. This is formed by forming the triazine ring by nitrogen being included in the main chain of the imino carbonate-based compound bonded to each other by heat.
- n is an integer of 1 to 100.
- Silver is a photocurable unsaturated functional group and a functional group derived from a compound having a hydroxy group or a carboxyl group, for example acrylic acid, methacrylic acid, butenoic acid, hexenoic acid, cinnamic acid, allylphenol, hydroxy It may be a functional group derived from a compound of styrene, hydroxycyclonuxene or hydroxynaphthoquinone. Specific examples of the above derived from acrylic acid It may be a functional group such as.
- R 2 is a functional group derived from a dicarboxylic acid compound Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, server acid, azelaic acid sebacic acid, norbornene dicarboxylic acid, cycloalkane dicarboxylic acid of C5-C10, and one member selected from the group consisting of an acid anhydride, or more compounds; Or phthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid, pyridine dica It may be a functional group derived from at least one compound selected from the group consisting of pyridine dicarboxylic acid, and acid anhydrides thereof.
- the coefficient of thermal expansion of the DFSR can be lowered to 30 or less for ⁇ and 150 or less for ⁇ 2. Due to this, the heat resistance reliability of the DFSR can be further improved, The difference in the coefficient of thermal expansion with the package substrate material of the semiconductor device can be reduced to minimize the warpage problem.
- the resin composition when cured, may have a coefficient of thermal expansion ( ⁇ ) of 10 to 35 ppm, preferably 20 ppm or less, before glass transition silver (Tg), and 150 ppm or less after glass transition temperature (Tg), Or 120 ppm or less, preferably 50 to 100 ppm of thermal expansion coefficient ( ⁇ 2).
- ⁇ coefficient of thermal expansion
- a DFSR which exhibits a lower coefficient of thermal expansion and improved heat resistance and can be preferably used as a package substrate material of a semiconductor device can be provided.
- the resin composition according to one embodiment will be described in more detail for each component.
- the resin composition of the embodiment includes a carboxyl group (-C00H) and an iminocarbonate-based compound having a photocurable unsaturated functional group as an acid-modified oligomer.
- Such acid-modified oligomers form crosslinks with other components of the resin composition, such as photopolymerizable monomers and / or thermosetting binders, by photocuring, thereby enabling the formation of DFSR, and the resin composition of the non-exposed portion, including the carboxyl group, is alkali developable.
- the resin composition includes the iminocarbonate-based compound as an acid-modified oligomer
- the triazine crosslinked structure represented by Chemical Formula 2 may be formed in the cured product of the resin composition forming DFSR.
- the resin composition of one embodiment enables the manufacture and provision of DFSR with higher glass transition temperature and improved heat resistance reliability.
- the iminocarbonate-based compound may be a compound formed by reacting a cyanate ester-based compound with a dicarboxylic acid compound and a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group.
- a bisphenol or novolac compound having a cyanide group (-0CN) for example, a compound of the formula la may be used:
- n is an integer of 1 to 100.
- the dicarboxylic acid compound reacting with the cyanate ester compound may be an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound or an aromatic dicarboxylic acid compound.
- the dicarboxylic acid compound is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, server acid, azelaic acid, sebacic acid, norbornene dicarboxylic acid, C5-C10 cyclo Alkanes (CYCL0ALKANE) dicarboxylic acids, acid anhydrides thereof or combinations of two or more of these compounds.
- CYCL0ALKANE C5-C10 cyclo Alkanes
- the dicarboxylic acid compound is a phthalic acid (phthalic acid), norbornene dicarboxyl ic acid (norbornene dicarboxyl ic acid), ⁇ tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid Acid (imidazole dicarboxyl ic acid), pyridine dicarboxylic acid, acid anhydrides thereof, or a combination of two or more of these compounds.
- Examples of the compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group include acrylic acid, methacrylic acid, cinnamic acid, butenoic acid, hexenoic acid, 2-allylphenol, and hydroxy.
- Styrene, hydroxycyclonuxene, hydroxy naphthoquinone (5-hydroxyl-p-naphthoquinone) or Two or more kinds thereof may be included.
- the dicarboxylic acid compound and the compound having a photocurable unsaturated functional group and a hydroxy group or a carboxyl group are reacted to form an acid-modified oligomer in which a carboxyl group and a photocurable unsaturated functional group are appropriately introduced.
- Iminocarbonate type compounds can be obtained preferably.
- the iminocarbonate-based compound thus obtained properly forms a triazine crosslinked structure during the thermosetting process, thereby enabling the formation and provision of DFSR exhibiting improved heat resistance reliability.
- the molar ratio of the carboxyl group introduced into the iminocarbonate-based compound and the unsaturated functional group is the molar ratio of the dicarboxylic acid compound to react with the cyanate ester-based compound and the compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group. It can be controlled and adjusted. In order to enable the imino carbonate-based compound to function properly as an acid-modified oligomer, the molar ratio of the dicarboxylic acid compound reacted with the cyanate ester-based compound and the compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group is About 2: 8 to 8: 2.
- the carboxyl group and the unsaturated functional group introduced therein are introduced into the iminocarbonate-based compound as the acid-side oligomer, and the resin composition of the non-exposed part exhibits excellent alkali developability, while the acid-modified oligomer is properly crosslinked with the photopolymerizable monomer and the thermosetting binder.
- the DFSR can exhibit more excellent heat resistance and mechanical properties.
- a compound formed by reacting a dicarboxylic acid compound, a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group with the acid-modified oligomer, in particular, the cyanate ester compound described above is It may be an iminocarbonate-based compound of formula 1:
- n is an integer of 1 to 100.
- silver is a functional group derived from a compound having a photocurable unsaturated and hydroxyl or carboxyl group, for example acrylic acid, methacrylic acid, butenoic acid, hexenmc acid, cinnamic acid, allylphenol, hydroxide From compounds of oxystyrene, hydroxyoxynucleene or hydroxynaphthoquinone
- R 2 is a functional group derived from a dicarboxylic acid compound, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, server acid, azelaic acid sebacic acid, norbornene dicarboxyl At least one compound selected from the group consisting of acids, C5-C10 cycloalkane (CYCL0ALKANE) dicarboxylic acids, and acid anhydrides thereof; Or phthalic acid, norbornene dicarboxylic acid, tetrahydrophthal ic acid, succinic acid, imidazole dicarboxylic acid, pyridine Functional groups derived from at least one compound selected from the group consisting of dicarboxylic acid (pyridine dicarboxylic acid), and acid anhydrides thereof;
- a dicarboxylic acid compound for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic
- Such a compound of the general formula (1) is, for example, a compound of the general formula la, a dicarboxylic acid compound such as phthalic acid, cyclonuclear dicarboxylic acid, tetrahydrophthalquaic acid, and unsaturated such as acrylic acid or 2-allylphenol. It can be obtained by reacting a compound having a functional group and a hydroxyl group or a carboxyl group, and can be suitably used as an acid-modified oligomer, while effectively forming a triazine crosslinked structure, thereby enabling the formation and provision of DFSR and the like having better heat resistance reliability. .
- the resin composition of one embodiment may further include a conventionally known acid-modified oligomer, in addition to the above-described iminocarbonate-based compound.
- a conventionally known acid-modified oligomer in addition to the above-described iminocarbonate-based compound.
- the already for the acid-modified oligomers of the furnace carbonate compound in the total weight of the resin composition from about 5 to 25 parts by weight 0/0, the black is to be included in an amount of about 7 to 20 weight 0/0, or from about 9 to 15% by weight
- it may include additional acid-modified oligomer of the remaining content of the total content of the acid-modified oligomer described below.
- Such additional acid-modified oligomers include carboxyl groups and photocurable functional groups, for example, photocurable functional groups having acrylate groups or unsaturated double bonds, and oligomers having carboxyl groups in the molecule. All ingredients known to be usable can be used without limitation.
- the main chain of such additional acid-modified oligomer may be a novolak epoxy or polyurethane, and the component in which a carboxyl group and an acrylate group are introduced into the main chain may be used as an additional acid-modified oligomer.
- the photocurable functional group may be preferably an acrylate group, wherein the acid-modified oligomer may be obtained as an oligomer form by copolymerizing a polymerizable monomer having a carboxyl group and a monomer including an acrylate compound. More specifically, ' specific examples of additional acid-modified oligomers usable in the resin composition include the following components:
- Organic acid (i) which has one carboxyl group and does not have an ethylenically unsaturated bond in 1 molecule, such as a C2-C17 alkylcarboxylic acid and an aromatic-group containing alkylcarboxylic acid, in the epoxy group of the copolymer of a (meth) acrylate.
- a carboxyl group-containing resin obtained by reacting the resulting secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d);
- diisocyanates (j) such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethyl butanoic acid (k), and poly carbonate-based polyols, polyether-based polyols, polyester-based polyol, polyolefin polyol, acrylic polyol, bisphenol a alkylene oxide adduct diol, a phenolic hydroxyl group and an "alkoeul St. compound having a hydroxyl group lights, etc.
- Carboxyl group-containing urethane resin obtained by polyaddition reaction of the diol compound ( m ) of this;
- a bifunctional epoxy resin such as an F type epoxy resin, a bisphenol S type epoxy resin, a bixenol type epoxy resin, and a biphenol type epoxy resin, and a carboxyl group-containing dialcohol compound (k) and the photosensitive carboxyl group-containing urethane resin obtained by the intermediate addition of a diol compound (m) by reaction;
- One isocyanate group or one or more isocyanate groups in a molecule such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin (7) or (8).
- Carboxyl group-containing urethane resin which added the compound which has a (meth) acryloyl group, and was terminal (meth) acrylated;
- Carboxyl group-containing photosensitive resin obtained by introducing an unsaturated double bond into the reaction product of a bisepoxy compound and bisphenols, and then reacting saturated or unsaturated polybasic anhydride (d);
- Novolak-type phenol resins alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and / or ethylene carbonate, propylene carbon
- the reaction product obtained by reacting unsaturated monocarboxylic acid (h) with a reaction product with cyclic carbonates such as carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate is saturated or unsaturated polybasic acid.
- Carboxyl group-containing photosensitive resin obtained by reacting anhydride (d);
- the isocyanate group containing compound used for resin synthesis does not contain a benzene ring.
- the linear structure in which the polyfunctional and bifunctional epoxy resins used for resin synthesis have a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, or a bixylenol skeleton
- a component which can be preferably used as an acid-modified oligomer can be obtained in view of flexibility of the DFSR.
- the modified product of the resins of the above (7) to (10) is preferable for the bending including the urethane bond in the main chain.
- the above-mentioned acid-modified oligomers can be included in an amount of about 15 to 75 weight 0/0, or from about 20 to 50 parts by weight 0/0, and black is about 25 to 45% by weight based on the total amount of one embodiment the resin composition have.
- the content of the acid-modified oligomer is too small, the developability of the resin composition may be lowered and the strength of the DFSR may be lowered.
- the resin composition may not only be excessively developed but also may be uneven during coating.
- the acid value of the acid-modified oligomer may be about 40 to 120 mgKOH / g, or About 50 to 110 mgKOH / g, or about 60 to 90 mgKOH / g. If the acid value is too low, alkali developability may be lowered. On the contrary, if the acid value is excessively high, since the developer may dissolve the photocurable portion, for example, the exposed portion, the normal pattern formation of the DFSR may be difficult.
- the resin composition of one embodiment includes a photopolymerizable monomer.
- a photopolymerizable monomer may be, for example, a compound having a photocurable unsaturated functional group such as two or more polyfunctional vinyl groups, and may form a crosslink with the unsaturated functional group of the acid-modified oligomer described above to provide photocuring during exposure.
- Crosslinked structure can be formed.
- a liquid phase can be used at room temperature, Accordingly, the viscosity of the resin composition of one embodiment may be adjusted to suit the coating method, or may also play a role of further improving alkali developability of the non-exposed part.
- an acrylate compound having two or more photocurable unsaturated functional groups may be used. More specifically, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol Hydroxyl group-containing acrylate compounds such as triacrylate or dipentaerythraltentaacrylate; Water-soluble acrylate compounds such as polyethylene glycol diacrylate or polypropylene glycol diacrylate; Polyfunctional polyester acrylate compounds of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythrane; Acrylate-based compounds of ethylene oxide adducts and / or propylene oxide adducts of polyfunctional alcohols such as trimethyl to propane or hydrogenated bisphenol A, or polyhydric phenols such as bisphenol k and biphenols; Polyfunctional or monofunctional polyurethane acrylate compounds which are isocyanate modified products of the
- the polyfunctional (meth) acrylate type compound which has two or more (meth) acryloyl groups in 1 molecule can be used preferably, Especially pentaerythritol triacrylate, trimethylol Propane triacrylate, dipentaerythr to nucleated acrylate, caprolactone modified ditrimethylol propane tetraacrylate, etc. Can be used.
- Examples of commercially available photopolymerizable monomers include Kaylarad's DPEA-12 and the like.
- the content of the photopolymerizable monomer described above may be about 5 to 30% by weight, or about 7 to 20% by weight, and black about 7 to 15% by weight based on the total weight of the resin composition.
- the photocuring may not be sufficient.
- the drying property of the DFSR may deteriorate and the physical properties may be degraded.
- the resin composition of one embodiment includes a photoinitiator.
- a photoinitiator serves to initiate radical photocuring between the acid-modified oligomer and the photopolymerizable monomer in the exposed portion of the resin composition.
- benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and its alkyl ether
- Acetophenones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone
- Thioxanthones such as 2, 4- dimethyl thioxanthone, 2, 4- diisopropyl thioxanthone, and 2-chloro thioxanthone
- Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal;
- oxime ester is mentioned as a preferable photoinitiator.
- Specific examples of oxime esters include 2- (acetyloxyiminomethyl) thioxanthene- 9-one, (1,2-octanedione, 1— [4- (phenylthio) phenyl]-, 2- (0_benzoyloxime ), (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)), and the like.
- GGI-325 manufactured by Chiba Specialty Chemical
- Irugacure OXE01 Irugacure 0XE02
- N-1919 manufactured by ADEKA
- Darocur TPO by Chiba Specialty Chemical
- the content of the photoinitiator may be about 0.5 to 20% by weight, or about 1 to 10% by weight, or about 1 to 5% by weight, based on the total weight of the resin composition.
- the content of the photoinitiator is too small, the photocuring may not occur properly, on the contrary, when the content of the photoinitiator is excessively large, the resolution of the resin composition may be lowered or the reliability of the DFSR may be insufficient.
- the resin composition of one embodiment also includes a thermosetting binder having at least one selected from among thermosetting functional groups such as epoxy groups, oxetanyl groups, cyclic ether groups and cyclic thio ether groups.
- a thermosetting binder having at least one selected from among thermosetting functional groups such as epoxy groups, oxetanyl groups, cyclic ether groups and cyclic thio ether groups.
- Such a thermosetting binder may form a crosslink with the acid-modified oligomer column by thermosetting to secure heat resistance or mechanical properties of the DFSR.
- thermosetting binder may have a softening point of about 70 to 100 ° C, thereby reducing the unevenness during lamination. Low softening points increase the tackiness of the DFSR, and high flow rates may deteriorate.
- thermosetting binder a resin having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in a molecule can be used, and a bifunctional epoxy resin can be used. have. Other diisocyanates or their difunctional block isocyanates can also be used.
- the thermosetting binder having two or more cyclic (thio) ether groups in the molecule is a 3, 4 or 5 member cyclic cyclic ether group, or cyclic in the molecule It may be a compound having two or more of any one or two kinds of thioether groups.
- the thermosetting binder may be a polyfunctional epoxy compound having at least two epoxy groups in a molecule, a polyfunctional oxetane compound having at least two oxetanyl groups in a molecule, or an episulfide resin having two or more thioether groups in a molecule And so on.
- the said polyfunctional epoxy compound bisphenol-A epoxy resin, hydrogenated bisphenol-A epoxy resin, brominated bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, novolak-type epoxy resin, for example Phenol phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, N-glycidyl-type epoxy resin, bisphenol A novolak-type epoxy resin, bixylenol-type epoxy resin, biphenol-type epoxy resin " , chelate type epoxy resin , Glyoxal type epoxy resin, amino group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone modified Epoxy resin, ⁇ - caprolactone modified epoxy resin, etc.
- novolak-type epoxy resin for example Phenol phenol novolak-type epoxy resin, cresol novolak-
- those in which atoms such as phosphorus are introduced into the structure may be used, and these epoxy resins are thermoset to improve properties such as adhesion of a cured film, solder heat resistance, and electroless plating resistance.
- polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy> methyl] ether, bis [(3-ethyl- 3-oxetanylmethoxy) methyl] ether, 1,4-bis [ (3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl Acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate.
- polyfunctional oxetanes such as oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly ( ⁇ -hydroxystyrene
- unsaturated monomers having an oxetane ring, alkyl (meth) acrylates examples include a copolymer.
- numerator bisphenol-A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example.
- episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used.
- YDCN-500-80P etc. of Kukdo Chemical Co., Ltd. can be used.
- thermosetting binder may be included in an amount corresponding to about 0.8 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer. If the content of the thermosetting binder is too small, carboxyl groups remain in the DFSR after curing, which may lower heat resistance, alkali resistance, electrical insulation, and the like. On the contrary, when the content is too large, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film and the like decrease.
- the resin composition of one embodiment includes a solvent; And at least one selected from the group consisting of a thermosetting binder catalyst, a filler, a pigment, and an additive to be described later.
- thermosetting binder catalyst serves to promote thermosetting of the thermosetting binder.
- thermosetting binder catalyst for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) - ⁇ , ⁇ -dimethylbenzylamine, 4-methoxy- ⁇ , ⁇ -dimethylbenzylamine, 4-methyl- ⁇ , ⁇ -dimethylbenzylamine compound; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc.
- 2 MOH-A, 2 MOH-0, 2 ⁇ , 2 ⁇ 4 ⁇ , 2 ⁇ 4 ⁇ (all brand names of an imidazole type compound) by Shikoku Kasei Kogyo Co., Ltd.
- U-CAT3503N and UCAT3502T by San Apro Corporation (All are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002C, all bicyclic amidine compounds and salts thereof; Can be mentioned.
- thermosetting catalyst of an epoxy resin or an oxetane compound may be the thermosetting catalyst of an epoxy resin or an oxetane compound, or it promotes reaction of an epoxy group and / or a moxetanyl group, and a carboxyl group, and can also be used individually or in combination of 2 or more types.
- guanamine, acetoguanamine, benzoguanamine, melamine 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-tri Azine, 2-vinyl-4, 6-diamino-S-triazine.
- Isocyanuric acid adduct 2,4-diamino-6-methacryloyloxyethyl-S-triazine ⁇ isocyanuric acid S-triazine derivatives, such as an adduct, can also be used,
- the compound which also functions as these adhesive imparting agents can be used together with the said thermosetting binder catalyst.
- thermosetting binder catalyst may be about 0.3 to 15 weight 3 ⁇ 4 with respect to the total weight of the resin composition in terms of appropriate thermosetting.
- the filler serves to improve heat stability, thermal dimensional stability and resin adhesion. In addition, it also serves as a constitution pigment by reinforcing the color.
- Inorganic or organic layer fillers may be used, for example barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide (alumina ), Aluminum hydroxide, mica and the like can be used.
- the content of the filler is preferably about 5 to 50% by weight based on the total weight of the composition. In the case of using more than 50 weight 3 ⁇ 4, the viscosity of the composition becomes high, so that the coating property is lowered or the degree of curing is not preferable.
- the pigments exhibit visibility and hiding power to hide defects such as scratches on circuit lines.
- red, blue, green, yellow, or dark pigment may be used.
- Phthalocyanine blue, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 60, etc. have.
- Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28 etc. can be used.
- the yellow pigments include anthraquinones, isoindolinones, condensed azos, and benzimidazolones.
- Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Pigment. Mention yellow 181, pigment yellow 193, etc. can be used.
- the content of the pigment is preferably used at about 0.5 to 3% by weight based on the total weight of the resin composition. When used in an amount less than 0.5%, visibility and hiding power are reduced, and when used in excess of 3% by weight, heat resistance is deteriorated.
- the additive may be added to remove bubbles of the resin composition or to remove popping or craters of the surface during coating of the film, to impart flame retardancy, to adjust viscosity, and to catalyst.
- known commonly used thickeners such as finely divided silica, organic bentonite and montmorillonite; Antifoaming agents and / or leveling agents such as silicone-based, fluorine-based and polymer-based; Silane coupling agents such as imidazole series, thiazole series, and triazole series;
- Known and common additives such as flame retardants such as phosphorus flame retardants and antimony flame retardants can be blended.
- the leveling agent serves to remove the popping and craters of the surface when the film is coated, for example, BYK-380N, BYK-307, BYK-307, BYK-378, BYK-350, etc. of BYK-Chemie GmbH.
- the content of the additive is preferably about 0.01 to 10% by weight based on the total weight of the resin composition.
- One or more solvents may be commonly used to dissolve the resin composition or impart an appropriate viscosity.
- Ketones such as methyl ethyl ketone and cyclonucleanone
- Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene
- Ethylene glycol monoethyl ether ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether
- Glycol ethers cellosolves
- Acetate esters such as dipropylene glycol monomethyl ether acetate
- Alcohols such as ethane, propanol, ethylene glycol, propylene glycol and carbyl
- Aliphatic hydrocarbons such as octane and decane
- Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha
- Amides such as dimethylacetamide and dimethylformamide (DMF), etc. are mentioned. These solvents can be used alone or as a mixture of two or more thereof.
- the content of the solvent may be about 10 to 50% by weight based on the total amount of the resin composition. If it is less than 10% by weight, the viscosity is high, the coating property is inferior, and when it exceeds 50% by weight, the drying is not good and stickiness increases.
- an acid-modified oligomer comprising a carboxy group (-C00H) and an iminocarbonate compound having a photocurable unsaturated functional group; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; And a cured product of a thermosetting binder having a thermosetting functional group may be provided.
- a photosensitive coating on the carrier film After applying the resin composition of the embodiment as a photosensitive coating materials, a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer coater, gravure coater or spray coater, etc., 50 to 130 After drying the oven at a temperature of 1 ° C. for 1 to 30 minutes and laminating a release film, a dry film composed of a carrier film, a photosensitive film, and a release film can be manufactured from below. .
- the thickness of the photosensitive film may be about 5 to about 100.
- a plastic film such as polyethylene terephthalate (PET), a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film may be used as the carrier film, and polyethylene (PE), A polytetrafluoroethylene film, a polypropylene film, a surface treated paper, etc. can be used, and when peeling a release film, it is preferable that the adhesive force of a photosensitive film and a release film is lower than the adhesive force of the photosensitive film and a carrier film.
- the photosensitive film layer is bonded onto the substrate on which the circuit is formed by using a vacuum laminator, hot laminator, vacuum press or the like.
- the substrate is exposed to light having a constant wavelength band (UV, etc.).
- the exposure may be selectively exposed with a photo mask or may be directly pattern exposed with a laser direct exposure machine.
- the carrier film peels off after exposure.
- exposure amount changes with coating film thickness 0-1,000 mJ / cuf is preferable.
- photocuring occurs in the exposure unit to form a crosslink between the acid-modified oligomer (for example, the iminocarbonate-based compound described above) and the unsaturated functional groups included in the photopolymerizable monomer. And as a result it can be left unremoved by subsequent phenomena.
- the non-exposed part may not be formed with the crosslinked structure and thus the crosslinked structure, and thus the carboxyl group may be maintained, and the non-exposed part may be in an alkali developable state.
- alkali The solution may be an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like. By this phenomenon, only the film of the exposed portion may remain.
- Heat curing (Post Cure) a printed circuit board including a solder resist formed from the photosensitive film is completed.
- Heat curing temperature is more than 100 ° C.
- the DFSR is an acid-modified oligomer comprising an iminocarbonate-based compound having a carboxyl group (-C00H) and a photocurable unsaturated functional group through photocuring and thermosetting; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; And a cured product of a thermosetting binder having a thermosetting functional group.
- the cured product may include a crosslinked structure in which the carboxyl group of the iminocarbonate-based compound and the thermosetting functional group are crosslinked by thermosetting; A crosslinked structure in which the unsaturated functional groups of the iminocarbonate compound and the photopolymerizable monomer are crosslinked by photocuring with each other; And it may include a triazine cross-linked structure of the formula (2) derived from the imino carbonate-based compound.
- the DFSR is higher than about 130 to 18 CTC, for example, about 140 to 170 ° C., or about 150 ° C.
- the DFSR can be suitably used as a package substrate material of a semiconductor device by satisfying various physical properties such as excellent PCT resistance, TCT heat resistance, and HAST resistance between fine wirings required for a package substrate material of a semiconductor device.
- the DFSR may further comprise a part in the photocuring and dispersing the remaining small amount of photoinitiators in the curing, water conditions.
- the dry film soldering resist may have a coefficient of thermal expansion ( ⁇ ) of 10 to 35 ppm, preferably 20 ppm or less, before the glass transition temperature (Tg), 150 ppm or less after the glass transition temperature (Tg), Or 120 ppm or less, preferably 50 to 100 ppm of thermal expansion coefficient ( ⁇ 2).
- ⁇ coefficient of thermal expansion
- the iminocarbonate-based compound of the acid-modified oligomer is composed of acrylic acid and 1,2,3,6-tetrahydrophthalic acid (4-Cyclohexene-l, 2-di car boxy) of the cyanate group of the bisphenol cyanate ester compound BA-230 of Lonza. lie acid) was reacted with a molar ratio of 1: 1 to prepare an iminocarbonate compound which is an acid-modified oligomer.
- thermosetting binder YDCN-500-80P 15% by weight of Japanese gunpowder, 2-PI 0.4% by weight of thermosetting binder catalyst, 3 ⁇ 4> 23% by weight of filler BaS0 4 , 0.3% by weight of additive phthalocyanine blue, 0.3% by weight of additive BYK-110, solvent DMF
- a resin composition was prepared by mixing 19% by weight.
- the resin composition prepared above was applied to PET as a carrier film, dried by passing through an oven at 75 ° C., and then laminated with PE as a release film, from below to a carrier film, a photosensitive film (thickness 20), and a release film.
- the dry film which consists of was manufactured.
- the photosensitive film layer was vacuum-laminated on the board
- Example 2 Except for using the imino carbonate compound 5 weight 3 ⁇ 4> (Example 2) or 15 weight% (Example 3), by increasing or decreasing the solvent content according to the increase or decrease of the content of the imino carbonate compound In the same manner as in Example 1, a dry film and a printed circuit board were manufactured. Examples 4-6
- a dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that DPHA of SK Cytec was not used as the photopolymerizable monomer. Comparative Example 5
- a dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that no thermosetting binder was used.
- Specific compositions of the resin compositions of Comparative Examples 1 to 5 are as summarized in Table 2 below.
- Test Example 1 PCT heat resistance and electroless nickel plating resistance
- Copper foil laminated sheet thickness 0.1 mm
- the film layer was vacuum laminated on a copper foil laminated plate (substrate) formed with a vacuum laminator (MV LP-500 manufactured by Meisei Seisakusho Co., Ltd.) And UV were exposed at an exposure dose of 350 mJ / cm 2 in the 365 nm wavelength band.
- the PET film was removed, developed with Na 2 C (1 wt% alkaline solution at 31 ° C. for a predetermined time, and photocured at an exposure dose of about 1000 mJ / cm 2. Finally, at about 170 ° C. for 1 hour.
- the specimen was prepared by heat curing.
- This specimen was treated for 192 hours under conditions of a temperature of 121 ° C., a humidity of 100% and a pressure of 2 atm using a PCT apparatus (spec Co., HAST system TPC-412MD), and observed the state of the coating film. The observations were evaluated based on the following criteria:
- Test Example 2 T g and the coefficient of thermal expansion
- the film layer was laminated
- TMA thermo mechanical analysis, METTLER TOLEDO, TMA / SDTA 840
- Glass transition temperature (Tg) was measured by the following method. First, the specimen was mounted on a holder to have a length of 10 mm, and the length of the specimen was measured under conditions of a temperature rising rate of 10 ° C / min from 50 ° C to 250 ° C with a force applied at both ends with 0.05 N. The inflection point seen in the temperature increase section was Tg, and Tg was evaluated by the following method:
- the said film layer was vacuum-laminated by the vacuum laminator (MVLP-500 by Meisei Seisakusho Co., Ltd.) on the copper foil laminated board (substrate) in which roughness was formed.
- a negative photo mask having a hole shape having a diameter of 80 was brought into close contact with each other, and UV of a 365 nm wavelength band was exposed at an exposure dose of 350 mJ / cm 2 .
- DFSR exhibited superior physical properties in comparison with the DFSR of the comparative example in not only developability but also various physical properties such as PCT heat resistance, glass transition temperature and thermal expansion coefficient. Therefore, it was confirmed that the example is suitable for the formation of DFSR showing high temperature heat resistance reliability.
Abstract
Description
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JP2014544685A JP5977361B2 (en) | 2012-02-20 | 2013-02-20 | Photocurable and thermosetting resin composition and dry film solder resist |
US14/379,720 US9389504B2 (en) | 2012-02-20 | 2013-02-20 | Photo-curable and thermo-curable resin composition, and dry film solder resist |
CN201380009949.1A CN104302708B (en) | 2012-02-20 | 2013-02-20 | Photocuring and the resin combination of heat cure and dry film solder mask |
US14/245,184 US9134609B2 (en) | 2012-02-20 | 2014-04-04 | Photo-curable and thermo-curable resin compostion, and dry film solder resist |
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KR10-2012-0083106 | 2012-07-30 | ||
KR1020120083106A KR101296851B1 (en) | 2012-07-30 | 2012-07-30 | Photo-curable and thermo-curable resin composition, and dry film solder resist |
KR10-2013-0008252 | 2013-01-24 | ||
KR1020130008252A KR101360968B1 (en) | 2012-03-19 | 2013-01-24 | Photo-curable and thermo-curable resin composition, and dry film solder resist |
KR1020130017683A KR101331573B1 (en) | 2012-02-20 | 2013-02-19 | Photo-curable and thermo-curable resin composition and dry film solder resist |
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