WO2018198921A1 - Composition, cured product, and method for producing cured product - Google Patents
Composition, cured product, and method for producing cured product Download PDFInfo
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- WO2018198921A1 WO2018198921A1 PCT/JP2018/016098 JP2018016098W WO2018198921A1 WO 2018198921 A1 WO2018198921 A1 WO 2018198921A1 JP 2018016098 W JP2018016098 W JP 2018016098W WO 2018198921 A1 WO2018198921 A1 WO 2018198921A1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Definitions
- the present invention relates to a composition having excellent gas barrier properties, a cured product, and a method for producing the cured product.
- Packaging materials typically used for packaging foods and beverages protect the contents from various distributions, storage such as refrigeration and processing such as heat sterilization, so that the strength, resistance to cracking, retort resistance, heat resistance
- functions such as properties
- a variety of functions are required, such as excellent transparency so that the contents can be confirmed.
- the required performance of plastic films used for packaging foods, pharmaceuticals, cosmetics, etc. includes barrier properties against various gases, transparency, retort resistance, impact resistance, flexibility, heat sealability, etc.
- a high barrier property against oxygen and water vapor is particularly required including conditions such as high humidity and after retorting.
- Such a gas barrier packaging material is usually constituted by laminating materials such as a flexible polymer film layer serving as a base material, a gas barrier layer, and a flexible polymer film layer serving as a sealant layer.
- a gas barrier material for forming a gas barrier layer vinylidene chloride having high retort resistance and gas or water vapor barrier properties has been frequently used.
- dioxin is generated at the time of disposal firing.
- polyvinyl alcohol resin or ethylene-polyvinyl alcohol copolymer is used as a barrier coating material, the oxygen barrier property is high under low humidity, but there is a problem that the oxygen barrier property is lowered under high humidity.
- An object of the present invention is to provide a composition that exhibits a high oxygen barrier property even under high humidity, and a cured product of the composition.
- the present inventors have found that in order to solve the above problems, the compound A represented by the following formula (1), the compound B represented by the following formula (2), and an aromatic ring or alicyclic structure And a compound C having two or more epoxy groups, wherein the molar ratio of epoxy groups to carboxyl groups in the composition is 0.1 to 1.8 I will provide a.
- X 1 represents an aromatic ring or alicyclic structure, and n1 and n2 each independently represents an integer of 0 to 3.
- composition whose compound C is a structure represented by following formula (3) is provided.
- X 2 represents an aromatic ring or alicyclic structure
- n3 represents an integer of 2 to 6
- R 2 independently represents a group represented by Formula (4) below.
- Y 1 and Y 3 each independently represent a divalent hydrocarbon group or an oxygen atom
- Y 2 represents a trivalent hydrocarbon group or a nitrogen atom
- n4 and n6 each independently represents 0 to 3 Represents an integer, n5 is 0 or 1, n7 is 1 when n5 is 0, and n7 is 2 when n5 is 1.
- the resin P obtained by reacting the compound A represented by the formula (1) and the compound B represented by the formula (2), an aromatic ring or alicyclic structure, and two or more epoxy groups The composition characterized by containing the compound C which has these.
- the process 1 which makes the compound A represented by the said Formula (1), the compound B represented by the said Formula (2) react, and obtains resin P, an aromatic ring or an alicyclic structure, and two or more
- a method for producing a cured product comprising the step 2 of reacting the compound C having an epoxy group with a resin P to obtain a cured product.
- composition of the present invention By providing the composition of the present invention, it is possible to provide a composition that exhibits high oxygen barrier properties even under high humidity, and a cured product of the composition. Moreover, since the composition of the present invention exhibits high barrier properties even under high humidity, it can be suitably used for coating agents, adhesives, gas barrier materials, and the like.
- the present invention relates to a compound A represented by the following formula (1), a compound B represented by the following formula (2), A composition comprising an aromatic or alicyclic structure and compound C having two or more epoxy groups, wherein the molar ratio of epoxy groups to carboxyl groups in the composition is 0.1 to 1.8.
- the composition characterized by these is provided.
- X 1 represents an aromatic ring or alicyclic structure, and n1 and n2 each independently represents an integer of 0 to 3.
- R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m1 to m3 each independently represents an integer of 0 to 3)
- Compound A of the present invention is a compound having an isocyanate group represented by the formula (1).
- X 1 represents an aromatic ring or alicyclic structure. By having an aromatic ring or alicyclic structure, a high barrier property can be exhibited.
- the aromatic ring structure is preferably an aromatic ring having 6 to 18 carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
- the aromatic ring may be substituted with at least one fluorine atom, and examples of the aromatic ring substituted with at least one fluorine atom include a perfluorophenyl group.
- the alicyclic structure is preferably an alicyclic ring having 3 to 20 carbon atoms, and may be a single ring or a condensed ring.
- cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, and the like.
- Monocyclic cycloalkenes include cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclooctene and the like.
- the condensed ring include bicycloundecane, decahydronaphthalene, norbornene, and norbornadiene.
- polycyclic compounds include cubane, basketan, and house. Moreover, you may be the ring structure which combined the aromatic ring and the alicyclic ring.
- X 1 is preferably a benzene ring or a naphthalene ring. Further, n1 and n2 are preferably each independently 0 to 1.
- the more preferable structure of compound A includes the following structures.
- Compound B of the present invention is a diol compound having a carboxyl group represented by the formula (2). By having a carboxyl group, it reacts with the compound C described later to form a crosslinked structure, and can exhibit high oxygen barrier properties under high humidity.
- Compound B is preferably a compound in which m3 is 0, and more preferably, R1 is a hydrocarbon group having 1 to 3 carbon atoms.
- Compound B More preferred structures of Compound B include dimethylolpropionic acid and dimethylolbutanoic acid.
- the compound C of the present invention is a compound having an aromatic ring or alicyclic structure and two or more epoxy groups.
- Compound C of the present invention can exhibit high barrier properties due to the aromatic ring or alicyclic structure.
- a crosslinked structure is formed by the reaction of the epoxy group and the carboxyl group of compound B, and a high oxygen barrier property under high humidity can be exhibited.
- Preferred structures of the compound C of the present invention include an alicyclic epoxy compound or a structure represented by the following formula (3).
- X 2 represents an aromatic ring or alicyclic structure
- n 3 represents an integer of 2 to 6
- R 2 independently represents a group represented by Formula (4) below
- Y 1 and Y 3 each independently represent a divalent hydrocarbon group or an oxygen atom
- Y 2 represents a trivalent hydrocarbon group or a nitrogen atom
- n4 and n6 each independently represents 0 to 3 Represents an integer, n5 is 0 or 1, n7 is 1 when n5 is 0, and n7 is 2 when n5 is 1.
- examples of the aromatic ring or alicyclic structure in X 2 include the same structures as the aromatic ring or alicyclic structure in compound A. Of these, a benzene ring, a naphthalene ring or a cycloalkane is preferred.
- Y 1 is an oxygen atom.
- particularly preferable structures include the following structures.
- the alicyclic epoxy group is preferably a cyclopentene oxide group or a cyclohexene oxide group.
- Particularly preferable structures include the following structures.
- the composition of the present invention is a composition containing Compound A, Compound B and Compound C, wherein the molar ratio of the epoxy group to the carboxyl group in the composition is 0.1 to 1.8. To do. When the molar ratio of the epoxy group to the carboxyl group is less than 0.1, the curability is poor and the moldability is deteriorated. When it is more than 1.8, the oxygen barrier property under high humidity becomes insufficient.
- the molar ratio of the epoxy group to the carboxyl group is preferably 0.1 to 1.5.
- the composition of the present invention comprises a resin P obtained by reacting compound A and compound B, and a compound C having an aromatic or alicyclic structure and two or more epoxy groups. It may be a thing. At this time, the molar ratio of the epoxy group to the carboxyl group in the composition is preferably 0.1 to 1.8.
- the composition of the present invention may contain a filler.
- a filler There is no limitation in particular as a filler, An inorganic filler and an organic filler are mentioned.
- the shape is not particularly limited, and may be various shapes such as a spherical shape, a granular shape, a rod shape, a needle shape, a fiber shape, a plate shape, and a woven / nonwoven shape.
- the aspect ratio can be high or low.
- fillers that improve barrier properties may be blended.
- it is a layered inorganic compound or a compound having an oxygen supplementing function.
- layered inorganic compounds include hydrous silicates (phyllosilicate minerals, etc.), kaolinite group clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.), and antigolite group clay minerals (antigolite). , Chrysotile, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), vermiculite group clay minerals (vermiculite, etc.), mica or mica group clay minerals (muscovite, gold) Mica such as mica, margarite, tetrasilic mica, and teniolite). These minerals may be natural clay minerals or synthetic clay minerals.
- a layered inorganic compound is used individually or in combination of 2 or more types.
- a preferred blending amount is 5-60% by mass of the layered clay mineral in the composition. More preferably, it is 5-50 mass%.
- Examples of the compound having an oxygen scavenging function include low molecular organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol, cobalt, manganese, nickel, iron, Examples include transition metal compounds such as copper.
- the composition may contain a solvent depending on the intended use.
- the solvent include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, methanol, ethanol, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol.
- examples thereof include monomethyl ether acetate. What is necessary is just to select the kind and usage-amount of a solvent suitably according to a use application.
- the composition may contain various additives as long as the effects of the present invention are not impaired.
- additives include various resins, reactive compounds, catalysts, polymerization initiators, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, waxes, surfactants, stabilizers, fluids
- regulators antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, compounds having an oxygen scavenging function, tackifiers, etc. it can.
- the composition of the present invention may contain a curing agent.
- a curing agent For example, when a compound having an epoxy group is blended, an amine curing agent, an amide curing agent, an acid anhydride curing agent.
- Various curing agents such as a phenolic curing agent, an active ester curing agent, a carboxyl group-containing curing agent and a thiol curing agent may be used in combination.
- the amine curing agents include diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenyl ether, diaminodiphenylsulfone, orthophenylenediamine, metaphenylenediamine, paraphenylenediamine, metaxylenediamine, paraxylenediamine, diethyltoluenediamine, diethylenetriamine. , Triethylenetetramine, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative, guanamine derivative and the like.
- amide-based curing agent examples include polyamide resins synthesized from dicyandiamide and a dimer of linolenic acid and ethylenediamine.
- acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexa And hydrophthalic anhydride.
- phenolic curing agents include bisphenol A, bisphenol F, bisphenol S, resorcin, catechol, hydroquinone, fluorene bisphenol, 4,4'-biphenol, 4,4 ', 4 "-trihydroxytriphenylmethane, naphthalenediol, 1 , 1,2,2-tetrakis (4-hydroxyphenyl) ethane, calixarene, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Xylok) Resin), polyhydric phenol novolak resin synthesized from formaldehyde and polyhydric hydroxy compound represented by resorcinol novolak resin, naphthol aralkyl resin, trimethylo Rumethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-
- a curing accelerator can be used.
- Various compounds that promote the curing reaction of the epoxy resin can be used as the curing accelerator, and examples thereof include phosphorus compounds, tertiary amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, and amine complex salts.
- the use of an imidazole compound, a phosphorus compound, and a tertiary amine compound is preferable, and particularly when used as a semiconductor sealing material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like.
- Triphenylphosphine is preferable for phosphorus compounds, and 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable for tertiary amines.
- the composition of the present invention can be cured.
- a hardening method What is necessary is just to use a well-known and usual method.
- thermal curing, thermal radical curing, etc. are mentioned.
- the composition containing Compound A, Compound B, and Compound C may be cured directly, or after creating a resin P obtained by reacting Compound A and Compound B, You may make it harden
- cure you may use together the hardening
- the molding method is arbitrary and may be selected as appropriate depending on the application. There is no restriction
- the composition is molded using, for example, an extrusion molding method, a plane press, a modified extrusion molding method, a blow molding method, a compression molding method, a vacuum molding method, an injection molding method, or the like.
- a method is mentioned.
- melt extrusion method, solution casting method, inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding examples include coating molding.
- the composition is cured with heat or active energy rays, the composition may be molded using various curing methods using heat or active energy rays.
- composition is liquid, it may be formed by coating.
- Coating methods include spray method, spin coating method, dipping method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, screen printing method, ink jet method, dispensing method, etc. Is mentioned.
- the laminate of the present invention is provided with a cured product layer obtained by curing the above-described composition on a substrate.
- the laminate may have a two-layer structure or a three-layer structure or more.
- the material of the base material is not particularly limited and may be appropriately selected depending on the application. Examples thereof include wood, metal, plastic, paper, silicon, modified silicon, and the like, which are obtained by joining different materials. There may be. There is no restriction
- the laminated body can be obtained by laminating the above-described molded body on the base material.
- the molded body laminated on the base material may be formed by direct coating or direct molding on the base material, or a molded body of the composition may be laminated.
- the coating method is not particularly limited, spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, A screen printing method, an inkjet method, etc. are mentioned.
- direct molding in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding and the like can be mentioned.
- laminating a molded product of the composition an uncured or semi-cured composition layer may be laminated on the substrate and then cured, or a cured product layer obtained by completely curing the composition is laminated on the substrate. May be.
- the laminate may be obtained by applying a substrate precursor to the cured layer of the composition and curing it, and the substrate precursor or composition is in an uncured or semi-cured state. It may be obtained by curing after bonding.
- a substrate precursor to the cured layer of the composition and curing it
- the substrate precursor or composition is in an uncured or semi-cured state. It may be obtained by curing after bonding.
- a precursor of a base material Various curable compositions etc. are mentioned.
- you may create a laminated body by using the composition which concerns on embodiment as an adhesive agent.
- composition of the present invention can be suitably used as a coating material or an adhesive. That is, the coating material or adhesive of the embodiment only needs to include the above-described composition.
- the composition of the present invention can be applied as a two-component type or a one-component type.
- the coating method for the coating material is not particularly limited, and examples of specific methods include various coating methods such as roll coating and gravure coating. Also, the coating apparatus is not particularly limited.
- the composition is excellent in adhesiveness, it can be suitably used as an adhesive.
- the form of the adhesive is not particularly limited, and may be a liquid or paste adhesive, or a solid adhesive. Since the composition has high gas barrier properties, this adhesive can be suitably used as a gas barrier adhesive.
- a liquid or paste-like adhesive it may be a one-component adhesive, or a two-component adhesive separately from a curing agent.
- the method of use is not particularly limited, but after application to one adhesive surface, the other adhesive surface may be bonded and bonded, or after injection at the interface of the adhesive surface Can be glued.
- an adhesive formed into a powder, chip, or sheet may be installed at the interface of the adhesive surface, and thermally bonded to be cured and cured.
- Example 1 10 parts by mass of polyurethane solution 1 prepared in Synthesis Example 1 and 1.6 parts by mass of resorcinol diglycidyl ether (trade name: Denacol EX201, manufactured by Nagase ChemteX Corporation) with respect to the carboxyl group of “DMPA / XDI” 1 equivalent group), 0.07 parts by mass of triphenylphosphine as a curing catalyst (1% by mass with respect to the total weight of the urethane resin and the epoxy resin), and 7.4 parts by mass of methanol, and a non-volatile content of 35% by mass A coating solution was prepared.
- PET polyethylene terephthalate
- E-5100 manufactured by Toyobo Co., Ltd.
- bar coater # 4 was applied to a 12 ⁇ m thick polyethylene terephthalate (PET) film (“E-5100” manufactured by Toyobo Co., Ltd.) with a bar coater # 4 and dried at 80 ° C. for 30 seconds to form a 2 ⁇ m film on the PET film. Further, curing was performed by heating in an oven at 80 ° C. for 24 hours, and the oxygen transmission rate of the obtained coating film 1 was measured. The results are shown in Table 1.
- Example 2 to [Example 5] Coating films 2 to 5 were obtained in the same manner as in Example 1 except that the formulations shown in Table 1 were changed. The blending amount and oxygen transmission rate are shown in Table 1.
- Comparative Example 3 A comparative coating film 3 was obtained in the same manner as in Comparative Example 2 except that the formulation shown in Table 1 was changed. The formulation and oxygen transmission rate are shown in Table 1.
- Denacol EX-201 Nagase ChemteX Corporation, resorcinol diglycidyl ether Celoxide 2021P: Daicel Corporation 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate
- TETRAD-X Mitsubishi Gas Chemical Co., Ltd., N, N, N ′, N′-tetraglycidyl-m-xylylenediamine / Denacol EX-810: manufactured by Nagase ChemteX Corporation, ethylene glycol diglycidyl ether
- composition of the present invention By providing the composition of the present invention, it is possible to provide a composition that exhibits high oxygen barrier properties even under high humidity, and a cured product of the composition. Moreover, since the composition of the present invention exhibits high barrier properties even under high humidity, it can be suitably used for coating agents, adhesives, gas barrier materials, and the like.
Abstract
Provided is a composition which comprises a compound A that has a specific structure containing an isocyanate group, a compound B that has a specific structure containing a hydroxyl group and a carboxyl group, and a compound C that has an aromatic ring or alicyclic structure and contains two or more epoxy groups, the composition being characterized in that the molar ratio of the epoxy groups to the carboxyl group in the composition is 0.1 to 1.8. Also provided is a composition characterized by comprising a compound A, a resin P that is obtained by being reacted with a compound B, and a compound C that has an aromatic ring or alicyclic structure and two or more epoxy groups.
Description
本発明は、ガスバリア性に優れた組成物、硬化物、および硬化物の製造方法に関する。
The present invention relates to a composition having excellent gas barrier properties, a cured product, and a method for producing the cured product.
食品や飲料等の包装に代表的に用いられる包装材料は、様々な流通、冷蔵等の保存や加熱殺菌などの処理等から内容物を保護するため、強度や割れにくさ、耐レトルト性、耐熱性といった機能ばかりでなく、内容物を確認できるよう透明性に優れるなど多岐に渡る機能が要求されており、透明性、軽量性、経済性等の理由からプラスチックフィルムや容器の使用が主流になっている。食品、医薬品、化粧品などの包装に用いられるプラスチックフィルムの要求性能としては、各種ガスに対するバリア性、透明性、耐レトルト処理性、耐衝撃性、柔軟性、ヒートシール性などが挙げられるが、内容物の性能あるいは性質を保持するという目的から、高湿度下やレトルト処理後などの条件下も含めた酸素および水蒸気に対する高いバリア性が特に要求されている。
Packaging materials typically used for packaging foods and beverages protect the contents from various distributions, storage such as refrigeration and processing such as heat sterilization, so that the strength, resistance to cracking, retort resistance, heat resistance In addition to functions such as properties, a variety of functions are required, such as excellent transparency so that the contents can be confirmed. For reasons such as transparency, lightness, and economy, the use of plastic films and containers has become the mainstream. ing. The required performance of plastic films used for packaging foods, pharmaceuticals, cosmetics, etc. includes barrier properties against various gases, transparency, retort resistance, impact resistance, flexibility, heat sealability, etc. For the purpose of maintaining the performance or properties of a product, a high barrier property against oxygen and water vapor is particularly required including conditions such as high humidity and after retorting.
このようなガスバリア性包装材料は、通常、基材となる可撓性ポリマーフィルム層、ガスバリア層、シーラント層となる可撓性ポリマーフィルム層などの各材料を積層させることにより構成されている。これらのうち、ガスバリア層を形成するガスバリア性材料としては、耐レトルト性及びガス又は水蒸気バリア性の高い塩化ビニリデンが多用されてきたが、廃棄の焼成時にダイオキシンが発生する等の問題がある。また、ポリビニルアルコール樹脂やエチレン－ポリビニルアルコール共重合体をバリアコーティング材料として用いた場合、低湿度下での酸素バリア性は高いが、高湿度下では酸素バリア性が低下する問題があった。
Such a gas barrier packaging material is usually constituted by laminating materials such as a flexible polymer film layer serving as a base material, a gas barrier layer, and a flexible polymer film layer serving as a sealant layer. Among these, as a gas barrier material for forming a gas barrier layer, vinylidene chloride having high retort resistance and gas or water vapor barrier properties has been frequently used. However, there is a problem that dioxin is generated at the time of disposal firing. Further, when polyvinyl alcohol resin or ethylene-polyvinyl alcohol copolymer is used as a barrier coating material, the oxygen barrier property is high under low humidity, but there is a problem that the oxygen barrier property is lowered under high humidity.
本発明の課題は、高湿度下であっても高い酸素バリア性を発揮する組成物、及び該組成物の硬化物を提供することにある。
An object of the present invention is to provide a composition that exhibits a high oxygen barrier property even under high humidity, and a cured product of the composition.
本発明者らは鋭意検討した結果、上記課題を解決するために、下記式（１）で表される化合物Ａと、下記式（２）で表される化合物Ｂと、芳香環または脂環構造と２個以上のエポキシ基を有する化合物Ｃとを含有する組成物であって、組成物中のカルボキシル基に対するエポキシ基のモル比率が０．１～１．８であることを特徴とする組成物を提供する。
As a result of intensive studies, the present inventors have found that in order to solve the above problems, the compound A represented by the following formula (1), the compound B represented by the following formula (2), and an aromatic ring or alicyclic structure And a compound C having two or more epoxy groups, wherein the molar ratio of epoxy groups to carboxyl groups in the composition is 0.1 to 1.8 I will provide a.
（式（１）において、Ｘ１は芳香環または脂環構造を表し、ｎ１およびｎ２はそれぞれ独立して０～３の整数を表す。）
(In Formula (1), X 1 represents an aromatic ring or alicyclic structure, and n1 and n2 each independently represents an integer of 0 to 3.)
（式（２）において、Ｒ１は水素原子または炭素数１～３の炭化水素基またはカルボニル基を表し、ｍ１～ｍ３はそれぞれ独立して０～３の整数を表す。）
(In Formula (2), R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m1 to m3 each independently represents an integer of 0 to 3)
また、化合物Ｃが、下記式（３）で表される構造である組成物を提供する。
Moreover, the composition whose compound C is a structure represented by following formula (3) is provided.
・・・（３）
... (3)
（式（３）において、Ｘ２は芳香環または脂環構造を表し、ｎ３は２～６の整数を表し、Ｒ２はそれぞれ独立して下記式（４）で表される基を表す。
(In Formula (3), X 2 represents an aromatic ring or alicyclic structure, n3 represents an integer of 2 to 6, and R 2 independently represents a group represented by Formula (4) below.
（Ｙ１およびＹ３はそれぞれ独立して２価の炭化水素基または酸素原子を表し、Ｙ２は３価の炭化水素基または窒素原子を表し、ｎ４およびｎ６はそれぞれ独立して０～３の整数を表し、ｎ５は０または１であって、ｎ５が０の時ｎ７は１であって、ｎ５が１の時ｎ７は２を表す。））
(Y 1 and Y 3 each independently represent a divalent hydrocarbon group or an oxygen atom, Y 2 represents a trivalent hydrocarbon group or a nitrogen atom, and n4 and n6 each independently represents 0 to 3 Represents an integer, n5 is 0 or 1, n7 is 1 when n5 is 0, and n7 is 2 when n5 is 1.)
また、前記式（１）で表される化合物Ａと、前記式（２）で表される化合物Ｂとを反応させて得られる樹脂Ｐと、芳香環または脂環構造と２個以上のエポキシ基を有する化合物Ｃとを含有することを特徴とする組成物を提供する。
Moreover, the resin P obtained by reacting the compound A represented by the formula (1) and the compound B represented by the formula (2), an aromatic ring or alicyclic structure, and two or more epoxy groups The composition characterized by containing the compound C which has these.
また、前記式（１）で表される化合物Ａと、前記式（２）で表される化合物Ｂとを反応させて樹脂Ｐを得る工程１と、芳香環または脂環構造と２個以上のエポキシ基を有する化合物Ｃと、樹脂Ｐとを反応させて硬化物を得る工程２とを有することを特徴とする、硬化物の製造方法を提供する。
Moreover, the process 1 which makes the compound A represented by the said Formula (1), the compound B represented by the said Formula (2) react, and obtains resin P, an aromatic ring or an alicyclic structure, and two or more There is provided a method for producing a cured product, comprising the step 2 of reacting the compound C having an epoxy group with a resin P to obtain a cured product.
本発明の組成物を提供することで、高湿度下であっても高い酸素バリア性を発揮する組成物、及び該組成物の硬化物を提供することが可能となる。また、本発明の組成物は、高湿度下であっても高いバリア性を示すことから、コーティング剤や接着剤、ガスバリア材料等に好適に使用可能である。
By providing the composition of the present invention, it is possible to provide a composition that exhibits high oxygen barrier properties even under high humidity, and a cured product of the composition. Moreover, since the composition of the present invention exhibits high barrier properties even under high humidity, it can be suitably used for coating agents, adhesives, gas barrier materials, and the like.
本発明は、下記式（１）で表される化合物Ａと、下記式（２）で表される化合物Ｂと、
芳香環または脂環構造と２個以上のエポキシ基を有する化合物Ｃとを含有する組成物であって、組成物中のカルボキシル基に対するエポキシ基のモル比率が０．１～１．８であることを特徴とする組成物を提供するものである。 The present invention relates to a compound A represented by the following formula (1), a compound B represented by the following formula (2),
A composition comprising an aromatic or alicyclic structure and compound C having two or more epoxy groups, wherein the molar ratio of epoxy groups to carboxyl groups in the composition is 0.1 to 1.8. The composition characterized by these is provided.
芳香環または脂環構造と２個以上のエポキシ基を有する化合物Ｃとを含有する組成物であって、組成物中のカルボキシル基に対するエポキシ基のモル比率が０．１～１．８であることを特徴とする組成物を提供するものである。 The present invention relates to a compound A represented by the following formula (1), a compound B represented by the following formula (2),
A composition comprising an aromatic or alicyclic structure and compound C having two or more epoxy groups, wherein the molar ratio of epoxy groups to carboxyl groups in the composition is 0.1 to 1.8. The composition characterized by these is provided.
（式（１）において、Ｘ１は芳香環または脂環構造を表し、ｎ１およびｎ２はそれぞれ独立して０～３の整数を表す。）
(In Formula (1), X 1 represents an aromatic ring or alicyclic structure, and n1 and n2 each independently represents an integer of 0 to 3.)
（式（２）において、Ｒ１は水素原子または炭素数１～３の炭化水素基またはカルボニル基を表し、ｍ１～ｍ３はそれぞれ独立して０～３の整数を表す。）
(In Formula (2), R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m1 to m3 each independently represents an integer of 0 to 3)
＜化合物Ａ＞
本発明の化合物Ａは、前記式（１）で表されるイソシアネート基を有する化合物である。化合物Ａにおいて、Ｘ１は芳香環または脂環構造を表す。芳香環または脂環構造を有することで、高いバリア性を発揮することが出来る。 <Compound A>
Compound A of the present invention is a compound having an isocyanate group represented by the formula (1). In compound A, X 1 represents an aromatic ring or alicyclic structure. By having an aromatic ring or alicyclic structure, a high barrier property can be exhibited.
本発明の化合物Ａは、前記式（１）で表されるイソシアネート基を有する化合物である。化合物Ａにおいて、Ｘ１は芳香環または脂環構造を表す。芳香環または脂環構造を有することで、高いバリア性を発揮することが出来る。 <Compound A>
Compound A of the present invention is a compound having an isocyanate group represented by the formula (1). In compound A, X 1 represents an aromatic ring or alicyclic structure. By having an aromatic ring or alicyclic structure, a high barrier property can be exhibited.
芳香環構造としては、炭素数６～１８の芳香環であることが好ましく、ベンゼン環、ナフタレン環、フェナントレン環、アントラセン環などが挙げられる。前記芳香環としては、少なくとも１つのフッ素原子により置換されていてもよく、少なくとも１つのフッ素原子で置換された芳香環としては、パーフルオロフェニル基などが挙げられる。
また、脂環構造としては炭素数３～２０の脂環が好ましく、単環であっても縮合環であってもかまわない。単環としては、シクロアルカンにはシクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン、シクロノナン、シクロデカン、シクロウンデカン、シクロドデカンなどがある。また、単環のシクロアルケンにはシクロプロペン、シクロブテン、シクロプロペン、シクロヘキセン、シクロヘプテン、シクロオクテンなどが挙げられる。縮合環としては、ビシクロウンデカンやデカヒドロナフタレン、ノルボルネンやノルボルナジエンなどがある。
また多環式化合物にはキュバン、バスケタン、ハウサン等が挙げられる。
また、芳香環と脂環を組み合わせた環構造であっても構わない。 The aromatic ring structure is preferably an aromatic ring having 6 to 18 carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. The aromatic ring may be substituted with at least one fluorine atom, and examples of the aromatic ring substituted with at least one fluorine atom include a perfluorophenyl group.
The alicyclic structure is preferably an alicyclic ring having 3 to 20 carbon atoms, and may be a single ring or a condensed ring. As monocycles, cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, and the like. Monocyclic cycloalkenes include cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclooctene and the like. Examples of the condensed ring include bicycloundecane, decahydronaphthalene, norbornene, and norbornadiene.
Examples of polycyclic compounds include cubane, basketan, and house.
Moreover, you may be the ring structure which combined the aromatic ring and the alicyclic ring.
また、脂環構造としては炭素数３～２０の脂環が好ましく、単環であっても縮合環であってもかまわない。単環としては、シクロアルカンにはシクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン、シクロノナン、シクロデカン、シクロウンデカン、シクロドデカンなどがある。また、単環のシクロアルケンにはシクロプロペン、シクロブテン、シクロプロペン、シクロヘキセン、シクロヘプテン、シクロオクテンなどが挙げられる。縮合環としては、ビシクロウンデカンやデカヒドロナフタレン、ノルボルネンやノルボルナジエンなどがある。
また多環式化合物にはキュバン、バスケタン、ハウサン等が挙げられる。
また、芳香環と脂環を組み合わせた環構造であっても構わない。 The aromatic ring structure is preferably an aromatic ring having 6 to 18 carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. The aromatic ring may be substituted with at least one fluorine atom, and examples of the aromatic ring substituted with at least one fluorine atom include a perfluorophenyl group.
The alicyclic structure is preferably an alicyclic ring having 3 to 20 carbon atoms, and may be a single ring or a condensed ring. As monocycles, cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, and the like. Monocyclic cycloalkenes include cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclooctene and the like. Examples of the condensed ring include bicycloundecane, decahydronaphthalene, norbornene, and norbornadiene.
Examples of polycyclic compounds include cubane, basketan, and house.
Moreover, you may be the ring structure which combined the aromatic ring and the alicyclic ring.
化合物Ａにおいて、Ｘ１は好ましくはベンゼン環またはナフタレン環である。
また、ｎ１およびｎ２はそれぞれ独立して０～１であることが好ましい。 In compound A, X 1 is preferably a benzene ring or a naphthalene ring.
Further, n1 and n2 are preferably each independently 0 to 1.
また、ｎ１およびｎ２はそれぞれ独立して０～１であることが好ましい。 In compound A, X 1 is preferably a benzene ring or a naphthalene ring.
Further, n1 and n2 are preferably each independently 0 to 1.
化合物Ａのさらに好ましい構造としては、以下の構造が挙げられる。
The more preferable structure of compound A includes the following structures.
＜化合物Ｂ＞
本発明の化合物Ｂは、前記式（２）で表される、カルボキシル基を有するジオール化合物である。カルボキシル基を有することで、後述する化合物Ｃと反応して架橋構造を形成し、高湿度下における高い酸素バリア性を発揮することが出来る。 <Compound B>
Compound B of the present invention is a diol compound having a carboxyl group represented by the formula (2). By having a carboxyl group, it reacts with the compound C described later to form a crosslinked structure, and can exhibit high oxygen barrier properties under high humidity.
本発明の化合物Ｂは、前記式（２）で表される、カルボキシル基を有するジオール化合物である。カルボキシル基を有することで、後述する化合物Ｃと反応して架橋構造を形成し、高湿度下における高い酸素バリア性を発揮することが出来る。 <Compound B>
Compound B of the present invention is a diol compound having a carboxyl group represented by the formula (2). By having a carboxyl group, it reacts with the compound C described later to form a crosslinked structure, and can exhibit high oxygen barrier properties under high humidity.
化合物Ｂにおいて、好ましくは、ｍ３が０である化合物であり、更に好ましくはＲ１が炭素数１～３の炭化水素基である場合である。
Compound B is preferably a compound in which m3 is 0, and more preferably, R1 is a hydrocarbon group having 1 to 3 carbon atoms.
化合物Ｂのさらに好ましい構造としては、ジメチロールプロピオン酸、及びジメチロールブタン酸が挙げられる。
More preferred structures of Compound B include dimethylolpropionic acid and dimethylolbutanoic acid.
＜化合物Ｃ＞
本発明の化合物Ｃは、芳香環または脂環構造と２個以上のエポキシ基を有する化合物である。本発明の化合物Ｃは、芳香環または脂環構造により高いバリア性を発揮できる。また、エポキシ基と化合物Ｂのカルボキシル基が反応することで架橋構造を形成し、高湿度下における高い酸素バリア性を発揮することが出来る。 <Compound C>
The compound C of the present invention is a compound having an aromatic ring or alicyclic structure and two or more epoxy groups. Compound C of the present invention can exhibit high barrier properties due to the aromatic ring or alicyclic structure. Moreover, a crosslinked structure is formed by the reaction of the epoxy group and the carboxyl group of compound B, and a high oxygen barrier property under high humidity can be exhibited.
本発明の化合物Ｃは、芳香環または脂環構造と２個以上のエポキシ基を有する化合物である。本発明の化合物Ｃは、芳香環または脂環構造により高いバリア性を発揮できる。また、エポキシ基と化合物Ｂのカルボキシル基が反応することで架橋構造を形成し、高湿度下における高い酸素バリア性を発揮することが出来る。 <Compound C>
The compound C of the present invention is a compound having an aromatic ring or alicyclic structure and two or more epoxy groups. Compound C of the present invention can exhibit high barrier properties due to the aromatic ring or alicyclic structure. Moreover, a crosslinked structure is formed by the reaction of the epoxy group and the carboxyl group of compound B, and a high oxygen barrier property under high humidity can be exhibited.
本発明の化合物Ｃの好ましい構造としては、脂環エポキシ化合物、または、以下の式（３）で表される構造が挙げられる。
Preferred structures of the compound C of the present invention include an alicyclic epoxy compound or a structure represented by the following formula (3).
・・・（３）
... (3)
（式（３）において、Ｘ２は芳香環または脂環構造を表し、ｎ３は２～６の整数を表し、Ｒ２はそれぞれ独立して下記式（４）で表される基を表す。）
(In Formula (3), X 2 represents an aromatic ring or alicyclic structure, n 3 represents an integer of 2 to 6, and R 2 independently represents a group represented by Formula (4) below)
（Ｙ１およびＹ３はそれぞれ独立して２価の炭化水素基または酸素原子を表し、Ｙ２は３価の炭化水素基または窒素原子を表し、ｎ４およびｎ６はそれぞれ独立して０～３の整数を表し、ｎ５は０または１であって、ｎ５が０の時ｎ７は１であって、ｎ５が１の時ｎ７は２を表す。））
(Y 1 and Y 3 each independently represent a divalent hydrocarbon group or an oxygen atom, Y 2 represents a trivalent hydrocarbon group or a nitrogen atom, and n4 and n6 each independently represents 0 to 3 Represents an integer, n5 is 0 or 1, n7 is 1 when n5 is 0, and n7 is 2 when n5 is 1.)
化合物Ｃが式（３）で表される構造の場合、Ｘ２における芳香環または脂環構造としては、前記化合物Ａにおける芳香環または脂環構造と同様の構造が挙げられる。中でも、ベンゼン環またはナフタレン環またはシクロアルカンである場合が好ましい。
When compound C has a structure represented by formula (3), examples of the aromatic ring or alicyclic structure in X 2 include the same structures as the aromatic ring or alicyclic structure in compound A. Of these, a benzene ring, a naphthalene ring or a cycloalkane is preferred.
化合物Ｃが式（３）で表される構造の場合、更に好ましくは、Ｙ１が酸素原子の場合である。
When compound C has a structure represented by formula (3), it is more preferable that Y 1 is an oxygen atom.
本発明の化合物Ｃが式（３）で表される構造の場合、特に好ましい構造としては、以下の構造が挙げられる。
In the case where the compound C of the present invention has a structure represented by the formula (3), particularly preferable structures include the following structures.
また、化合物Ｃが脂環エポキシ化合物である場合、脂環エポキシ基がシクロペンテンオキシド基またはシクロヘキセンオキシド基であると好ましい。
特に好ましい構造としては、以下の構造が挙げられる。 When compound C is an alicyclic epoxy compound, the alicyclic epoxy group is preferably a cyclopentene oxide group or a cyclohexene oxide group.
Particularly preferable structures include the following structures.
特に好ましい構造としては、以下の構造が挙げられる。 When compound C is an alicyclic epoxy compound, the alicyclic epoxy group is preferably a cyclopentene oxide group or a cyclohexene oxide group.
Particularly preferable structures include the following structures.
＜組成物＞
本発明の組成物は、化合物Ａと化合物Ｂと化合物Ｃとを含有する組成物であり、組成物中のカルボキシル基に対するエポキシ基のモル比率が０．１～１．８であることを特徴とする。
カルボキシル基に対するエポキシ基のモル比率が０．１未満である場合、硬化性に劣り成形性が悪化する。１．８より多い場合、高湿度下での酸素バリア性が不十分となる。
カルボキシル基に対するエポキシ基のモル比率は、好ましくは０．１～１．５である。 <Composition>
The composition of the present invention is a composition containing Compound A, Compound B and Compound C, wherein the molar ratio of the epoxy group to the carboxyl group in the composition is 0.1 to 1.8. To do.
When the molar ratio of the epoxy group to the carboxyl group is less than 0.1, the curability is poor and the moldability is deteriorated. When it is more than 1.8, the oxygen barrier property under high humidity becomes insufficient.
The molar ratio of the epoxy group to the carboxyl group is preferably 0.1 to 1.5.
本発明の組成物は、化合物Ａと化合物Ｂと化合物Ｃとを含有する組成物であり、組成物中のカルボキシル基に対するエポキシ基のモル比率が０．１～１．８であることを特徴とする。
カルボキシル基に対するエポキシ基のモル比率が０．１未満である場合、硬化性に劣り成形性が悪化する。１．８より多い場合、高湿度下での酸素バリア性が不十分となる。
カルボキシル基に対するエポキシ基のモル比率は、好ましくは０．１～１．５である。 <Composition>
The composition of the present invention is a composition containing Compound A, Compound B and Compound C, wherein the molar ratio of the epoxy group to the carboxyl group in the composition is 0.1 to 1.8. To do.
When the molar ratio of the epoxy group to the carboxyl group is less than 0.1, the curability is poor and the moldability is deteriorated. When it is more than 1.8, the oxygen barrier property under high humidity becomes insufficient.
The molar ratio of the epoxy group to the carboxyl group is preferably 0.1 to 1.5.
本発明の組成物は、化合物Ａと化合物Ｂとを反応させて得られる樹脂Ｐと、芳香環または脂環構造と２個以上のエポキシ基を有する化合物Ｃとを含有することを特徴とする組成物であってもよい。このとき、組成物中のカルボキシル基に対するエポキシ基のモル比率が０．１～１．８であることが好ましい。化合物Ａと化合物Ｂとを反応させて樹脂Ｐを先に合成しておく場合、工程数は増えるものの、副反応が起こりにくいため、最終的な硬化物の均一性が向上する。
The composition of the present invention comprises a resin P obtained by reacting compound A and compound B, and a compound C having an aromatic or alicyclic structure and two or more epoxy groups. It may be a thing. At this time, the molar ratio of the epoxy group to the carboxyl group in the composition is preferably 0.1 to 1.8. When compound A and compound B are reacted to synthesize resin P first, the number of steps is increased, but side reactions are unlikely to occur, so the uniformity of the final cured product is improved.
＜フィラー＞
本発明の組成物は、フィラーを含有しても構わない。フィラーとしては特に限定は無く、無機フィラーと有機フィラーが挙げられる。形状についても特に限定は無く、球状、粒状、棒状、針状、繊維状、板状、織布・不織布状等、様々な形状であって構わない。アスペクト比が高くても低くてもかまわない。 <Filler>
The composition of the present invention may contain a filler. There is no limitation in particular as a filler, An inorganic filler and an organic filler are mentioned. The shape is not particularly limited, and may be various shapes such as a spherical shape, a granular shape, a rod shape, a needle shape, a fiber shape, a plate shape, and a woven / nonwoven shape. The aspect ratio can be high or low.
本発明の組成物は、フィラーを含有しても構わない。フィラーとしては特に限定は無く、無機フィラーと有機フィラーが挙げられる。形状についても特に限定は無く、球状、粒状、棒状、針状、繊維状、板状、織布・不織布状等、様々な形状であって構わない。アスペクト比が高くても低くてもかまわない。 <Filler>
The composition of the present invention may contain a filler. There is no limitation in particular as a filler, An inorganic filler and an organic filler are mentioned. The shape is not particularly limited, and may be various shapes such as a spherical shape, a granular shape, a rod shape, a needle shape, a fiber shape, a plate shape, and a woven / nonwoven shape. The aspect ratio can be high or low.
更なるバリア性を付与するために、バリア性を向上させるフィラーを配合しても構わない。例えば、層状無機化合物や酸素補足機能を有する化合物等である。
In order to impart further barrier properties, fillers that improve barrier properties may be blended. For example, it is a layered inorganic compound or a compound having an oxygen supplementing function.
層状無機化合物としては、例えば、含水ケイ酸塩（フィロケイ酸塩鉱物等）、カオリナイト族粘土鉱物（ハロイサイト、カオリナイト、エンデライト、ディッカイト、ナクライト等）、アンチゴライト族粘土鉱物（アンチゴライト、クリソタイル等）、スメクタイト族粘土鉱物（モンモリロナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト、ソーコナイト、スティーブンサイト等）、バーミキュライト族粘土鉱物（バーミキュライト等）、雲母又はマイカ族粘土鉱物（白雲母、金雲母等の雲母、マーガライト、テトラシリリックマイカ、テニオライト等）が挙げられる。これらの鉱物は天然粘土鉱物であっても合成粘土鉱物であってもよい。層状無機化合物は単独でまたは二種以上組み合わせて使用される。
Examples of layered inorganic compounds include hydrous silicates (phyllosilicate minerals, etc.), kaolinite group clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.), and antigolite group clay minerals (antigolite). , Chrysotile, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), vermiculite group clay minerals (vermiculite, etc.), mica or mica group clay minerals (muscovite, gold) Mica such as mica, margarite, tetrasilic mica, and teniolite). These minerals may be natural clay minerals or synthetic clay minerals. A layered inorganic compound is used individually or in combination of 2 or more types.
層状粘土鉱物を配合する場合、好ましい配合量としては、組成物中において層状粘土鉱物が５－６０質量％である。更に好ましくは５－５０質量％である。
When the layered clay mineral is blended, a preferred blending amount is 5-60% by mass of the layered clay mineral in the composition. More preferably, it is 5-50 mass%.
酸素捕捉機能を有する化合物としては、例えば、ヒンダードフェノール類、ビタミンＣ、ビタミンＥ、有機燐化合物、没食子酸、ピロガロール等の酸素と反応する低分子有機化合物や、コバルト、マンガン、ニッケル、鉄、銅等の遷移金属化合物等が挙げられる。
Examples of the compound having an oxygen scavenging function include low molecular organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol, cobalt, manganese, nickel, iron, Examples include transition metal compounds such as copper.
＜配合物＞
組成物は、使用用途に応じて溶剤を含有してもよい。溶剤としては有機溶剤が挙げられ、例えばメチルエチルケトン、アセトン、酢酸エチル、酢酸ブチル、トルエン、ジメチルホルムアミド、アセトニトリル、メチルイソブチルケトン、メタノール、エタノール、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。溶剤の種類及び使用量は使用用途によって適宜選択すればよい。 <Formulation>
The composition may contain a solvent depending on the intended use. Examples of the solvent include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, methanol, ethanol, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol. Examples thereof include monomethyl ether acetate. What is necessary is just to select the kind and usage-amount of a solvent suitably according to a use application.
組成物は、使用用途に応じて溶剤を含有してもよい。溶剤としては有機溶剤が挙げられ、例えばメチルエチルケトン、アセトン、酢酸エチル、酢酸ブチル、トルエン、ジメチルホルムアミド、アセトニトリル、メチルイソブチルケトン、メタノール、エタノール、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。溶剤の種類及び使用量は使用用途によって適宜選択すればよい。 <Formulation>
The composition may contain a solvent depending on the intended use. Examples of the solvent include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, methanol, ethanol, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol. Examples thereof include monomethyl ether acetate. What is necessary is just to select the kind and usage-amount of a solvent suitably according to a use application.
組成物は、本発明の効果を損なわない範囲で、各種の添加剤を含有してもよい。添加剤としては、例えば、各種樹脂、反応性化合物、触媒、重合開始剤、安定剤（酸化防止剤、熱安定剤、紫外線吸収剤等）、可塑剤、ワックス、界面活性剤、安定剤、流動調整剤、帯電防止剤、滑剤、ブロッキング防止剤、着色剤、結晶核剤、カップリング剤、染料、レベリング剤、レオロジーコントロール剤、紫外線吸収剤、酸素捕捉機能を有する化合物、粘着付与剤等が例示できる。
The composition may contain various additives as long as the effects of the present invention are not impaired. Examples of additives include various resins, reactive compounds, catalysts, polymerization initiators, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, waxes, surfactants, stabilizers, fluids Examples include regulators, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, compounds having an oxygen scavenging function, tackifiers, etc. it can.
また、本発明の組成物は、硬化剤を配合してもよい、例えば、エポキシ基を有する化合物を配合している場合には、アミン系硬化剤、アミド系硬化剤、酸無水物系硬化剤、フェノール系硬化剤、活性エステル系硬化剤、カルボキシル基含有硬化剤、チオール系硬化剤などの各種の硬化剤を併用してもかまわない。
The composition of the present invention may contain a curing agent. For example, when a compound having an epoxy group is blended, an amine curing agent, an amide curing agent, an acid anhydride curing agent. Various curing agents such as a phenolic curing agent, an active ester curing agent, a carboxyl group-containing curing agent and a thiol curing agent may be used in combination.
具体的には、アミン系硬化剤としてはジアミノジフェニルメタン、ジアミノジフェニルエタン、ジアミノジフェニルエーテル、ジアミノジフェニルスルホン、オルトフェニレンジアミン、メタフェニレンジアミン、パラフェニレンジアミン、メタキシレンジアミン、パラキシレンジアミン、ジエチルトルエンジアミン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、イミダゾ－ル、ＢＦ３－アミン錯体、グアニジン誘導体、グアナミン誘導体等が挙げられる。
Specifically, the amine curing agents include diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenyl ether, diaminodiphenylsulfone, orthophenylenediamine, metaphenylenediamine, paraphenylenediamine, metaxylenediamine, paraxylenediamine, diethyltoluenediamine, diethylenetriamine. , Triethylenetetramine, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative, guanamine derivative and the like.
アミド系硬化剤としては、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂等が挙げられる。
酸無水物系硬化剤としては、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。
フェノール系硬化剤としては、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、レゾルシン、カテコール、ハイドロキノン、フルオレンビスフェノール、４，４’－ビフェノール、４，４’，４”－トリヒドロキシトリフェニルメタン、ナフタレンジオール、１，１，２，２－テトラキス（４－ヒドロキシフェニル）エタン、カリックスアレーン、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂（ザイロック樹脂）、レゾルシンノボラック樹脂に代表される多価ヒドロキシ化合物とホルムアルデヒドから合成される多価フェノールノボラック樹脂、ナフトールアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール－フェノール共縮ノボラック樹脂、ナフトール－クレゾール共縮ノボラック樹脂、ビフェニル変性フェノール樹脂（ビスメチレン基でフェノール核が連結された多価フェノール化合物）、ビフェニル変性ナフトール樹脂（ビスメチレン基でフェノール核が連結された多価ナフトール化合物）、アミノトリアジン変性フェノール樹脂（メラミン、ベンゾグアナミンなどでフェノール核が連結された多価フェノール化合物）やアルコキシ基含有芳香環変性ノボラック樹脂（ホルムアルデヒドでフェノール核及びアルコキシ基含有芳香環が連結された多価フェノール化合物）等の多価フェノール化合物が挙げられる。
これらの硬化剤は、単独でも２種類以上の併用でも構わない。 Examples of the amide-based curing agent include polyamide resins synthesized from dicyandiamide and a dimer of linolenic acid and ethylenediamine.
Examples of acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexa And hydrophthalic anhydride.
Examples of phenolic curing agents include bisphenol A, bisphenol F, bisphenol S, resorcin, catechol, hydroquinone, fluorene bisphenol, 4,4'-biphenol, 4,4 ', 4 "-trihydroxytriphenylmethane, naphthalenediol, 1 , 1,2,2-tetrakis (4-hydroxyphenyl) ethane, calixarene, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Xylok) Resin), polyhydric phenol novolak resin synthesized from formaldehyde and polyhydric hydroxy compound represented by resorcinol novolak resin, naphthol aralkyl resin, trimethylo Rumethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyphenol compound in which phenol nucleus is linked by bismethylene group), biphenyl Modified naphthol resin (polyvalent naphthol compound with phenol nucleus linked by bismethylene group), aminotriazine modified phenolic resin (polyvalent phenol compound with phenol nucleus linked by melamine, benzoguanamine, etc.) or alkoxy group-containing aromatic ring modified novolak resin Examples thereof include polyhydric phenol compounds such as (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
These curing agents may be used alone or in combination of two or more.
酸無水物系硬化剤としては、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。
フェノール系硬化剤としては、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、レゾルシン、カテコール、ハイドロキノン、フルオレンビスフェノール、４，４’－ビフェノール、４，４’，４”－トリヒドロキシトリフェニルメタン、ナフタレンジオール、１，１，２，２－テトラキス（４－ヒドロキシフェニル）エタン、カリックスアレーン、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂（ザイロック樹脂）、レゾルシンノボラック樹脂に代表される多価ヒドロキシ化合物とホルムアルデヒドから合成される多価フェノールノボラック樹脂、ナフトールアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール－フェノール共縮ノボラック樹脂、ナフトール－クレゾール共縮ノボラック樹脂、ビフェニル変性フェノール樹脂（ビスメチレン基でフェノール核が連結された多価フェノール化合物）、ビフェニル変性ナフトール樹脂（ビスメチレン基でフェノール核が連結された多価ナフトール化合物）、アミノトリアジン変性フェノール樹脂（メラミン、ベンゾグアナミンなどでフェノール核が連結された多価フェノール化合物）やアルコキシ基含有芳香環変性ノボラック樹脂（ホルムアルデヒドでフェノール核及びアルコキシ基含有芳香環が連結された多価フェノール化合物）等の多価フェノール化合物が挙げられる。
これらの硬化剤は、単独でも２種類以上の併用でも構わない。 Examples of the amide-based curing agent include polyamide resins synthesized from dicyandiamide and a dimer of linolenic acid and ethylenediamine.
Examples of acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexa And hydrophthalic anhydride.
Examples of phenolic curing agents include bisphenol A, bisphenol F, bisphenol S, resorcin, catechol, hydroquinone, fluorene bisphenol, 4,4'-biphenol, 4,4 ', 4 "-trihydroxytriphenylmethane, naphthalenediol, 1 , 1,2,2-tetrakis (4-hydroxyphenyl) ethane, calixarene, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Xylok) Resin), polyhydric phenol novolak resin synthesized from formaldehyde and polyhydric hydroxy compound represented by resorcinol novolak resin, naphthol aralkyl resin, trimethylo Rumethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyphenol compound in which phenol nucleus is linked by bismethylene group), biphenyl Modified naphthol resin (polyvalent naphthol compound with phenol nucleus linked by bismethylene group), aminotriazine modified phenolic resin (polyvalent phenol compound with phenol nucleus linked by melamine, benzoguanamine, etc.) or alkoxy group-containing aromatic ring modified novolak resin Examples thereof include polyhydric phenol compounds such as (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
These curing agents may be used alone or in combination of two or more.
また、硬化促進剤を使用することもできる。硬化促進剤としてはエポキシ樹脂の硬化反応を促す種々の化合物が使用でき、例えば、リン系化合物、第３級アミン化合物、イミダゾール化合物、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。この中でも、イミダゾール化合物、リン系化合物、第３級アミン化合物の使用が好ましく、特に半導体封止材料用途として使用する場合には、硬化性、耐熱性、電気特性、耐湿信頼性等に優れる点から、リン系化合物ではトリフェニルホスフィン、第３級アミンでは１，８－ジアザビシクロ－［５．４．０］－ウンデセン（ＤＢＵ）が好ましい。
Also, a curing accelerator can be used. Various compounds that promote the curing reaction of the epoxy resin can be used as the curing accelerator, and examples thereof include phosphorus compounds, tertiary amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, and amine complex salts. Among these, the use of an imidazole compound, a phosphorus compound, and a tertiary amine compound is preferable, and particularly when used as a semiconductor sealing material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like. Triphenylphosphine is preferable for phosphorus compounds, and 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable for tertiary amines.
＜硬化物＞
本発明の組成物は、硬化させることができる。硬化方法としては特に限定は無く、公知慣用の方法を用いればよい。例えば、熱硬化や熱ラジカル硬化等が挙げられる。
本発明の組成物を硬化させる場合、化合物Ａと化合物Ｂと化合物Ｃとを含有する組成物を直接硬化させてもよいし、化合物Ａと化合物Ｂとを反応させた樹脂Ｐを作成した後、化合物Ｃと反応させることで硬化させてもよい。また、硬化させる際には前述した硬化剤や硬化促進剤を併用しても構わない。 <Hardened product>
The composition of the present invention can be cured. There is no limitation in particular as a hardening method, What is necessary is just to use a well-known and usual method. For example, thermal curing, thermal radical curing, etc. are mentioned.
When curing the composition of the present invention, the composition containing Compound A, Compound B, and Compound C may be cured directly, or after creating a resin P obtained by reacting Compound A and Compound B, You may make it harden | cure by making it react with the compound C. Moreover, when making it harden | cure, you may use together the hardening | curing agent and hardening accelerator which were mentioned above.
本発明の組成物は、硬化させることができる。硬化方法としては特に限定は無く、公知慣用の方法を用いればよい。例えば、熱硬化や熱ラジカル硬化等が挙げられる。
本発明の組成物を硬化させる場合、化合物Ａと化合物Ｂと化合物Ｃとを含有する組成物を直接硬化させてもよいし、化合物Ａと化合物Ｂとを反応させた樹脂Ｐを作成した後、化合物Ｃと反応させることで硬化させてもよい。また、硬化させる際には前述した硬化剤や硬化促進剤を併用しても構わない。 <Hardened product>
The composition of the present invention can be cured. There is no limitation in particular as a hardening method, What is necessary is just to use a well-known and usual method. For example, thermal curing, thermal radical curing, etc. are mentioned.
When curing the composition of the present invention, the composition containing Compound A, Compound B, and Compound C may be cured directly, or after creating a resin P obtained by reacting Compound A and Compound B, You may make it harden | cure by making it react with the compound C. Moreover, when making it harden | cure, you may use together the hardening | curing agent and hardening accelerator which were mentioned above.
上述した組成物を成形することで成形体を製造することが可能である。成形方法は任意であり、用途によって適時選択すればよい。成形体の形状に制限はなく、板状、シート状、又はフィルム状であってもよく、立体形状を有していてもよく、基材に塗布されたものであってもよく、基材と基材の間に存在する形で成形されたものであってもよい。
It is possible to produce a molded body by molding the composition described above. The molding method is arbitrary and may be selected as appropriate depending on the application. There is no restriction | limiting in the shape of a molded object, A plate shape, a sheet form, or a film form may be sufficient, it may have a three-dimensional shape, and what was apply | coated to the base material, What was shape | molded in the form which exists between base materials may be sufficient.
板状、シート状の成形体を製造する場合、例えば押し出し成形法、平面プレス、異形押し出し成形法、ブロー成形法、圧縮成形法、真空成形法、射出成形法等を用いて組成物を成形する方法が挙げられる。また、フィルム状の成形体を製造する場合、例えば溶融押出法、溶液キャスト法、インフレーションフィルム成形、キャスト成形、押出ラミネーション成形、カレンダー成形、シート成形、繊維成形、ブロー成形、射出成形、回転成形、被覆成形が挙げられる。熱や活性エネルギー線で硬化する組成物である場合、熱や活性エネルギー線を用いた各種硬化方法を用いて組成物を成形してもよい。
When producing a plate-like or sheet-like molded body, the composition is molded using, for example, an extrusion molding method, a plane press, a modified extrusion molding method, a blow molding method, a compression molding method, a vacuum molding method, an injection molding method, or the like. A method is mentioned. In the case of producing a film-like molded product, for example, melt extrusion method, solution casting method, inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, Examples include coating molding. When the composition is cured with heat or active energy rays, the composition may be molded using various curing methods using heat or active energy rays.
組成物が液状である場合、塗工により成形してもよい。塗工方法としては、スプレー法、スピンコート法、ディップ法、ロールコート法、ブレードコート法、ドクターロール法、ドクターブレード法、カーテンコート法、スリットコート法、スクリーン印刷法、インクジェット法、ディスペンス法等が挙げられる。
If the composition is liquid, it may be formed by coating. Coating methods include spray method, spin coating method, dipping method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, screen printing method, ink jet method, dispensing method, etc. Is mentioned.
本発明の積層体は上述した組成物を硬化した硬化物層を基材上に備えるものである。積層体は２層構造であってもよく３層構造以上であってもよい。
The laminate of the present invention is provided with a cured product layer obtained by curing the above-described composition on a substrate. The laminate may have a two-layer structure or a three-layer structure or more.
基材の材質は特に限定はなく、用途に応じて適宜選択すればよく、例えば木材、金属、プラスチック、紙、シリコン又は変性シリコン等が挙げられ、異なる素材を接合して得られた基材であってもよい。基材の形状は特に制限はなく、平板、シート状、又は３次元形状全面に、若しくは一部に、曲率を有するもの等目的に応じた任意の形状であってよい。また、基材の硬度、厚み等にも制限はない。
The material of the base material is not particularly limited and may be appropriately selected depending on the application. Examples thereof include wood, metal, plastic, paper, silicon, modified silicon, and the like, which are obtained by joining different materials. There may be. There is no restriction | limiting in particular in the shape of a base material, You may be arbitrary shapes according to the objectives, such as what has a flat plate, a sheet form, or a three-dimensional shape whole surface, or a part, a curvature. Moreover, there is no restriction | limiting also in the hardness of a base material, thickness, etc.
積層体は、基材上に上述した成形体を積層することで得ることができる。基材上に積層する成形体は、基材に対し直接塗工又は直接成形により形成してもよく、組成物の成形体を積層してもよい。直接塗工する場合、塗工方法としては特に限定はなく、スプレー法、スピンコート法、ディップ法、ロールコート法、ブレードコート法、ドクターロール法、ドクターブレード法、カーテンコート法、スリットコート法、スクリーン印刷法、インクジェット法等が挙げられる。直接成形する場合は、インモールド成形、インサート成形、真空成形、押出ラミネート成形、プレス成形等が挙げられる。組成物の成形体を積層する場合、未硬化又は半硬化の組成物層を基材上に積層してから硬化させてもよく、組成物を完全硬化した硬化物層を基材上に積層してもよい。
The laminated body can be obtained by laminating the above-described molded body on the base material. The molded body laminated on the base material may be formed by direct coating or direct molding on the base material, or a molded body of the composition may be laminated. When coating directly, the coating method is not particularly limited, spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, A screen printing method, an inkjet method, etc. are mentioned. In the case of direct molding, in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding and the like can be mentioned. When laminating a molded product of the composition, an uncured or semi-cured composition layer may be laminated on the substrate and then cured, or a cured product layer obtained by completely curing the composition is laminated on the substrate. May be.
また、積層体は、組成物の硬化物層に対して基材の前駆体を塗工して硬化させることで得てもよく、基材の前駆体又は組成物が未硬化若しくは半硬化の状態で接着させた後に硬化させて得てもよい。基材の前駆体としては特に限定はなく、各種硬化性組成物等が挙げられる。また、実施形態に係る組成物を接着剤として用いることで積層体を作成してもよい。
In addition, the laminate may be obtained by applying a substrate precursor to the cured layer of the composition and curing it, and the substrate precursor or composition is in an uncured or semi-cured state. It may be obtained by curing after bonding. There is no limitation in particular as a precursor of a base material, Various curable compositions etc. are mentioned. Moreover, you may create a laminated body by using the composition which concerns on embodiment as an adhesive agent.
本発明の組成物は、コーティング材又は接着剤として好適に用いることができる。すなわち、実施形態のコーティング材又は接着剤は、上述した組成物を含むものであればよい。なお、本発明の組成物は２液型としても１液型としても適用できる。
The composition of the present invention can be suitably used as a coating material or an adhesive. That is, the coating material or adhesive of the embodiment only needs to include the above-described composition. The composition of the present invention can be applied as a two-component type or a one-component type.
コーティング材のコーティング方法としては特に制限されないが、具体的な方法としては、ロールコート、グラビアコート等の各種コーティング方法を例示することができる。また、コーティング装置についても特に限定されない。
The coating method for the coating material is not particularly limited, and examples of specific methods include various coating methods such as roll coating and gravure coating. Also, the coating apparatus is not particularly limited.
組成物は、接着性に優れるため、接着剤として好適に用いることができる。接着剤の形態には特に限定はなく、液状又はペースト状の接着剤としてもよく、固形状の接着剤としてもよい。組成物は、高いガスバリア性を有することから、この接着剤はガスバリア用接着剤として好適に利用可能である。
Since the composition is excellent in adhesiveness, it can be suitably used as an adhesive. The form of the adhesive is not particularly limited, and may be a liquid or paste adhesive, or a solid adhesive. Since the composition has high gas barrier properties, this adhesive can be suitably used as a gas barrier adhesive.
液状又はペースト状の接着剤の場合、１液型の接着剤としてもよく、硬化剤を別にした２液型の接着剤としてもよい。液状又はペースト状の接着剤の場合は、使用方法としては特に限定はないが、一方の接着面に塗布後、他方の接着面を貼り合わせ、接着させて良く、または接着面の界面に注入後、接着させてよい。
In the case of a liquid or paste-like adhesive, it may be a one-component adhesive, or a two-component adhesive separately from a curing agent. In the case of a liquid or paste-like adhesive, the method of use is not particularly limited, but after application to one adhesive surface, the other adhesive surface may be bonded and bonded, or after injection at the interface of the adhesive surface Can be glued.
固形状の接着剤の場合は、粉末状、チップ状、又はシート状に成形した接着剤を、接着面の界面に設置し、熱溶解させることで接着し、硬化させてよい。
In the case of a solid adhesive, an adhesive formed into a powder, chip, or sheet may be installed at the interface of the adhesive surface, and thermally bonded to be cured and cured.
以下、実施例により、本発明をさらに具体的に説明するが、本発明はこれに限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
［合成例１］
撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、ＤＭＰＡ（２，２－ジメチロールプロパン酸、東京化成製）９０質量部、溶媒としてメチルエチルケトン５４質量部、テトラヒドロフラン８１質量部を仕込み、窒素気流下にて攪拌した。次いで、ＸＤＩ（キシリレンジイソシアネート、商品名：タケネート５００、三井化学製）５６質量部を仕込み、６０℃に昇温した。１時間撹拌した後、４０℃以下まで温度を下げてから、更にＸＤＩ５６質量部を仕込み、再度６０℃に昇温した。赤外分光法でイソシアネート基の消失が確認されるまで反応を継続した。次いで、樹脂の不揮発分量が５０質量％となるように希釈溶媒としてメタノールを加え、カルボキシル基を含有するウレタン樹脂「ＤＭＰＡ／ＸＤＩ」を含有するポリウレタン溶液１を得た。 [Synthesis Example 1]
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 90 parts by mass of DMPA (2,2-dimethylolpropanoic acid, manufactured by Tokyo Chemical Industry), 54 parts by mass of methyl ethyl ketone as a solvent, and 81 parts by mass of tetrahydrofuran. The mixture was stirred under a nitrogen stream. Next, 56 parts by mass of XDI (xylylene diisocyanate, trade name: Takenate 500, manufactured by Mitsui Chemicals) was charged, and the temperature was raised to 60 ° C. After stirring for 1 hour, the temperature was lowered to 40 ° C. or lower, and 56 parts by mass of XDI was further charged, and the temperature was raised to 60 ° C. again. The reaction was continued until the disappearance of the isocyanate group was confirmed by infrared spectroscopy. Next, methanol was added as a diluent solvent so that the nonvolatile content of the resin was 50% by mass, and a polyurethane solution 1 containing a urethane resin “DMPA / XDI” containing a carboxyl group was obtained.
撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、ＤＭＰＡ（２，２－ジメチロールプロパン酸、東京化成製）９０質量部、溶媒としてメチルエチルケトン５４質量部、テトラヒドロフラン８１質量部を仕込み、窒素気流下にて攪拌した。次いで、ＸＤＩ（キシリレンジイソシアネート、商品名：タケネート５００、三井化学製）５６質量部を仕込み、６０℃に昇温した。１時間撹拌した後、４０℃以下まで温度を下げてから、更にＸＤＩ５６質量部を仕込み、再度６０℃に昇温した。赤外分光法でイソシアネート基の消失が確認されるまで反応を継続した。次いで、樹脂の不揮発分量が５０質量％となるように希釈溶媒としてメタノールを加え、カルボキシル基を含有するウレタン樹脂「ＤＭＰＡ／ＸＤＩ」を含有するポリウレタン溶液１を得た。 [Synthesis Example 1]
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 90 parts by mass of DMPA (2,2-dimethylolpropanoic acid, manufactured by Tokyo Chemical Industry), 54 parts by mass of methyl ethyl ketone as a solvent, and 81 parts by mass of tetrahydrofuran. The mixture was stirred under a nitrogen stream. Next, 56 parts by mass of XDI (xylylene diisocyanate, trade name: Takenate 500, manufactured by Mitsui Chemicals) was charged, and the temperature was raised to 60 ° C. After stirring for 1 hour, the temperature was lowered to 40 ° C. or lower, and 56 parts by mass of XDI was further charged, and the temperature was raised to 60 ° C. again. The reaction was continued until the disappearance of the isocyanate group was confirmed by infrared spectroscopy. Next, methanol was added as a diluent solvent so that the nonvolatile content of the resin was 50% by mass, and a polyurethane solution 1 containing a urethane resin “DMPA / XDI” containing a carboxyl group was obtained.
［実施例１］
合成例１で作製したポリウレタン溶液１を１０質量部、レゾルシノールジグリシジルエーテル（商品名：デナコールＥＸ２０１、ナガセケムテックス社製）を１．６質量部（「ＤＭＰＡ／ＸＤＩ」のカルボキシル基に対してエポキシ基が１当量）、硬化触媒としてトリフェニルホスフィンを０．０７質量部（ウレタン樹脂とエポキシ樹脂の合計重量に対して１質量％）、メタノールを７．４質量部配合して不揮発分３５質量％の塗布液を調製した。これを１２μｍ厚のポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡（株）製 「Ｅ－５１００」）にバーコータ＃４で塗布し、８０℃で３０秒乾燥して２μｍの膜をＰＥＴフィルム上に作製した。さらに８０℃のオーブンで２４時間加熱して硬化を進行させ、得られたコーティングフィルム１の酸素透過率を測定した。結果は表１に記した。 [Example 1]
10 parts by mass of polyurethane solution 1 prepared in Synthesis Example 1 and 1.6 parts by mass of resorcinol diglycidyl ether (trade name: Denacol EX201, manufactured by Nagase ChemteX Corporation) with respect to the carboxyl group of “DMPA / XDI” 1 equivalent group), 0.07 parts by mass of triphenylphosphine as a curing catalyst (1% by mass with respect to the total weight of the urethane resin and the epoxy resin), and 7.4 parts by mass of methanol, and a non-volatile content of 35% by mass A coating solution was prepared. This was applied to a 12 μm thick polyethylene terephthalate (PET) film (“E-5100” manufactured by Toyobo Co., Ltd.) with a bar coater # 4 and dried at 80 ° C. for 30 seconds to form a 2 μm film on the PET film. Further, curing was performed by heating in an oven at 80 ° C. for 24 hours, and the oxygen transmission rate of the obtained coating film 1 was measured. The results are shown in Table 1.
合成例１で作製したポリウレタン溶液１を１０質量部、レゾルシノールジグリシジルエーテル（商品名：デナコールＥＸ２０１、ナガセケムテックス社製）を１．６質量部（「ＤＭＰＡ／ＸＤＩ」のカルボキシル基に対してエポキシ基が１当量）、硬化触媒としてトリフェニルホスフィンを０．０７質量部（ウレタン樹脂とエポキシ樹脂の合計重量に対して１質量％）、メタノールを７．４質量部配合して不揮発分３５質量％の塗布液を調製した。これを１２μｍ厚のポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡（株）製 「Ｅ－５１００」）にバーコータ＃４で塗布し、８０℃で３０秒乾燥して２μｍの膜をＰＥＴフィルム上に作製した。さらに８０℃のオーブンで２４時間加熱して硬化を進行させ、得られたコーティングフィルム１の酸素透過率を測定した。結果は表１に記した。 [Example 1]
10 parts by mass of polyurethane solution 1 prepared in Synthesis Example 1 and 1.6 parts by mass of resorcinol diglycidyl ether (trade name: Denacol EX201, manufactured by Nagase ChemteX Corporation) with respect to the carboxyl group of “DMPA / XDI” 1 equivalent group), 0.07 parts by mass of triphenylphosphine as a curing catalyst (1% by mass with respect to the total weight of the urethane resin and the epoxy resin), and 7.4 parts by mass of methanol, and a non-volatile content of 35% by mass A coating solution was prepared. This was applied to a 12 μm thick polyethylene terephthalate (PET) film (“E-5100” manufactured by Toyobo Co., Ltd.) with a bar coater # 4 and dried at 80 ° C. for 30 seconds to form a 2 μm film on the PET film. Further, curing was performed by heating in an oven at 80 ° C. for 24 hours, and the oxygen transmission rate of the obtained coating film 1 was measured. The results are shown in Table 1.
＜酸素透過率の測定＞
前記で得られたコーティングフィルム１を、モコン社製酸素透過率測定装置ＯＸ－ＴＲＡＮ１／５０を用いて、２３℃ ９０％ＲＨの雰囲気下で測定した。なお、ＲＨは相対湿度を示す。得られたコーティングフィルムの透過率から以下の式（ａ）を用いてコーティング膜単体の透過率を算出した。さらに、実測の塗布量から５ｇ／ｍ２当たりの酸素透過率に換算した。
１／Ｐ＝１／Ｐ１＋１／Ｐ２ ・・・（ａ）
Ｐ ：コーティングフィルムの酸素透過率
Ｐ１：塗膜単体の酸素透過率
Ｐ２：１２μｍＰＥＴフィルムの酸素透過率 <Measurement of oxygen permeability>
The coating film 1 obtained above was measured in an atmosphere of 23 ° C. and 90% RH using an oxygen permeability measuring device OX-TRAN1 / 50 manufactured by Mocon. Note that RH indicates relative humidity. From the transmittance of the obtained coating film, the transmittance of the coating film alone was calculated using the following formula (a). Furthermore, the oxygen transmission rate per 5 g / m 2 was converted from the actually applied amount.
1 / P = 1 / P1 + 1 / P2 (a)
P: oxygen transmission rate of coating film P1: oxygen transmission rate of coating film alone P2: oxygen transmission rate of 12 μm PET film
前記で得られたコーティングフィルム１を、モコン社製酸素透過率測定装置ＯＸ－ＴＲＡＮ１／５０を用いて、２３℃ ９０％ＲＨの雰囲気下で測定した。なお、ＲＨは相対湿度を示す。得られたコーティングフィルムの透過率から以下の式（ａ）を用いてコーティング膜単体の透過率を算出した。さらに、実測の塗布量から５ｇ／ｍ２当たりの酸素透過率に換算した。
１／Ｐ＝１／Ｐ１＋１／Ｐ２ ・・・（ａ）
Ｐ ：コーティングフィルムの酸素透過率
Ｐ１：塗膜単体の酸素透過率
Ｐ２：１２μｍＰＥＴフィルムの酸素透過率 <Measurement of oxygen permeability>
The coating film 1 obtained above was measured in an atmosphere of 23 ° C. and 90% RH using an oxygen permeability measuring device OX-TRAN1 / 50 manufactured by Mocon. Note that RH indicates relative humidity. From the transmittance of the obtained coating film, the transmittance of the coating film alone was calculated using the following formula (a). Furthermore, the oxygen transmission rate per 5 g / m 2 was converted from the actually applied amount.
1 / P = 1 / P1 + 1 / P2 (a)
P: oxygen transmission rate of coating film P1: oxygen transmission rate of coating film alone P2: oxygen transmission rate of 12 μm PET film
［実施例２］～［実施例５］
表１記載の配合物に変更した以外は実施例１と同様の方法にて、コーティングフィルム２～５を得た。配合量および酸素透過率は表１に記した。 [Example 2] to [Example 5]
Coating films 2 to 5 were obtained in the same manner as in Example 1 except that the formulations shown in Table 1 were changed. The blending amount and oxygen transmission rate are shown in Table 1.
表１記載の配合物に変更した以外は実施例１と同様の方法にて、コーティングフィルム２～５を得た。配合量および酸素透過率は表１に記した。 [Example 2] to [Example 5]
Coating films 2 to 5 were obtained in the same manner as in Example 1 except that the formulations shown in Table 1 were changed. The blending amount and oxygen transmission rate are shown in Table 1.
［比較例１］
合成例１で作製したポリウレタン溶液１を１０質量部、メタノールを４．３質量部配合して不揮発分３５質量％の塗布液を調製した。これを１２μｍ厚のＰＥＴフィルム（東洋紡（株）製 「Ｅ－５１００」）にバーコータ＃４で塗布し、８０℃で３０秒乾燥して２μｍの膜をＰＥＴ上に作製し、得られた比較コーティングフィルム１の酸素透過率を測定した。結果は表１に記した。 [Comparative Example 1]
10 parts by mass of the polyurethane solution 1 prepared in Synthesis Example 1 and 4.3 parts by mass of methanol were blended to prepare a coating solution having a nonvolatile content of 35% by mass. This was applied to a 12 μm-thick PET film (“E-5100” manufactured by Toyobo Co., Ltd.) with a bar coater # 4 and dried at 80 ° C. for 30 seconds to produce a 2 μm film on the PET. The oxygen transmission rate of the film 1 was measured. The results are shown in Table 1.
合成例１で作製したポリウレタン溶液１を１０質量部、メタノールを４．３質量部配合して不揮発分３５質量％の塗布液を調製した。これを１２μｍ厚のＰＥＴフィルム（東洋紡（株）製 「Ｅ－５１００」）にバーコータ＃４で塗布し、８０℃で３０秒乾燥して２μｍの膜をＰＥＴ上に作製し、得られた比較コーティングフィルム１の酸素透過率を測定した。結果は表１に記した。 [Comparative Example 1]
10 parts by mass of the polyurethane solution 1 prepared in Synthesis Example 1 and 4.3 parts by mass of methanol were blended to prepare a coating solution having a nonvolatile content of 35% by mass. This was applied to a 12 μm-thick PET film (“E-5100” manufactured by Toyobo Co., Ltd.) with a bar coater # 4 and dried at 80 ° C. for 30 seconds to produce a 2 μm film on the PET. The oxygen transmission rate of the film 1 was measured. The results are shown in Table 1.
［比較例２］
合成例１で作製したポリウレタン溶液１を１０質量部、レゾルシノールジグリシジルエーテル（商品名：デナコールＥＸ２０１、ナガセケムテックス社製）を３．３質量部（「ＤＭＰＡ／ＸＤＩ」のカルボキシル基に対してエポキシ基が２当量）、硬化触媒としてトリフェニルホスフィンを０．０８質量部（ウレタン樹脂とエポキシ樹脂の合計重量に対して１質量％）、メタノールを１１質量部配合して不揮発分３５質量％の塗布液を調製した。これを１２μｍ厚のＰＥＴフィルム（東洋紡（株）製 「Ｅ－５１００」）にバーコータ＃４で塗布し、８０℃で３０秒乾燥して２μｍの膜をＰＥＴフィルム上に作製した。さらに８０℃のオーブンで２４時間加熱して硬化を進行させ、得られた比較コーティングフィルム２の酸素透過率を測定した。結果は表１に記した。 [Comparative Example 2]
10 parts by mass of polyurethane solution 1 prepared in Synthesis Example 1 and 3.3 parts by mass of resorcinol diglycidyl ether (trade name: Denacol EX201, manufactured by Nagase ChemteX Corporation) with respect to the carboxyl group of “DMPA / XDI” 2 equivalents), 0.08 parts by weight of triphenylphosphine as a curing catalyst (1% by weight with respect to the total weight of urethane resin and epoxy resin), and 11 parts by weight of methanol. A liquid was prepared. This was coated on a 12 μm thick PET film (“E-5100” manufactured by Toyobo Co., Ltd.) with a bar coater # 4 and dried at 80 ° C. for 30 seconds to form a 2 μm film on the PET film. Furthermore, it heated for 24 hours in 80 degreeC oven, hardening was advanced, and the oxygen permeability of the obtained comparative coating film 2 was measured. The results are shown in Table 1.
合成例１で作製したポリウレタン溶液１を１０質量部、レゾルシノールジグリシジルエーテル（商品名：デナコールＥＸ２０１、ナガセケムテックス社製）を３．３質量部（「ＤＭＰＡ／ＸＤＩ」のカルボキシル基に対してエポキシ基が２当量）、硬化触媒としてトリフェニルホスフィンを０．０８質量部（ウレタン樹脂とエポキシ樹脂の合計重量に対して１質量％）、メタノールを１１質量部配合して不揮発分３５質量％の塗布液を調製した。これを１２μｍ厚のＰＥＴフィルム（東洋紡（株）製 「Ｅ－５１００」）にバーコータ＃４で塗布し、８０℃で３０秒乾燥して２μｍの膜をＰＥＴフィルム上に作製した。さらに８０℃のオーブンで２４時間加熱して硬化を進行させ、得られた比較コーティングフィルム２の酸素透過率を測定した。結果は表１に記した。 [Comparative Example 2]
10 parts by mass of polyurethane solution 1 prepared in Synthesis Example 1 and 3.3 parts by mass of resorcinol diglycidyl ether (trade name: Denacol EX201, manufactured by Nagase ChemteX Corporation) with respect to the carboxyl group of “DMPA / XDI” 2 equivalents), 0.08 parts by weight of triphenylphosphine as a curing catalyst (1% by weight with respect to the total weight of urethane resin and epoxy resin), and 11 parts by weight of methanol. A liquid was prepared. This was coated on a 12 μm thick PET film (“E-5100” manufactured by Toyobo Co., Ltd.) with a bar coater # 4 and dried at 80 ° C. for 30 seconds to form a 2 μm film on the PET film. Furthermore, it heated for 24 hours in 80 degreeC oven, hardening was advanced, and the oxygen permeability of the obtained comparative coating film 2 was measured. The results are shown in Table 1.
［比較例３］
表１記載の配合物に変更した以外は比較例２と同様の方法にて比較コーティングフィルム３を得た。配合および酸素透過率は表１に記した。 [Comparative Example 3]
A comparative coating film 3 was obtained in the same manner as in Comparative Example 2 except that the formulation shown in Table 1 was changed. The formulation and oxygen transmission rate are shown in Table 1.
表１記載の配合物に変更した以外は比較例２と同様の方法にて比較コーティングフィルム３を得た。配合および酸素透過率は表１に記した。 [Comparative Example 3]
A comparative coating film 3 was obtained in the same manner as in Comparative Example 2 except that the formulation shown in Table 1 was changed. The formulation and oxygen transmission rate are shown in Table 1.
表中で使用した材料は以下の通り。
・デナコールＥＸ－２０１：ナガセケムテックス（株）製、レゾルシノールジグリシジルエーテル
・セロキサイド２０２１Ｐ：（株）ダイセル製、３’，４’－エポキシシクロヘキシルメチル３，４－エポキシシクロヘキサンカルボキシレート
・ＴＥＴＲＡＤ－Ｘ：三菱ガス化学（株）製、N,N,N',N'-テトラグリシジル-m-キシリレンジアミン
・デナコールＥＸ－８１０：ナガセケムテックス（株）製、エチレングリコールジグリシジルエーテル The materials used in the table are as follows.
Denacol EX-201: Nagase ChemteX Corporation, resorcinol diglycidyl ether Celoxide 2021P: Daicel Corporation 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate TETRAD-X: Mitsubishi Gas Chemical Co., Ltd., N, N, N ′, N′-tetraglycidyl-m-xylylenediamine / Denacol EX-810: manufactured by Nagase ChemteX Corporation, ethylene glycol diglycidyl ether
・デナコールＥＸ－２０１：ナガセケムテックス（株）製、レゾルシノールジグリシジルエーテル
・セロキサイド２０２１Ｐ：（株）ダイセル製、３’，４’－エポキシシクロヘキシルメチル３，４－エポキシシクロヘキサンカルボキシレート
・ＴＥＴＲＡＤ－Ｘ：三菱ガス化学（株）製、N,N,N',N'-テトラグリシジル-m-キシリレンジアミン
・デナコールＥＸ－８１０：ナガセケムテックス（株）製、エチレングリコールジグリシジルエーテル The materials used in the table are as follows.
Denacol EX-201: Nagase ChemteX Corporation, resorcinol diglycidyl ether Celoxide 2021P: Daicel Corporation 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate TETRAD-X: Mitsubishi Gas Chemical Co., Ltd., N, N, N ′, N′-tetraglycidyl-m-xylylenediamine / Denacol EX-810: manufactured by Nagase ChemteX Corporation, ethylene glycol diglycidyl ether
本発明の組成物を提供することで、高湿度下であっても高い酸素バリア性を発揮する組成物、及び該組成物の硬化物を提供することが可能となる。また、本発明の組成物は、高湿度下であっても高いバリア性を示すことから、コーティング剤や接着剤、ガスバリア材料等に好適に使用可能である。
By providing the composition of the present invention, it is possible to provide a composition that exhibits high oxygen barrier properties even under high humidity, and a cured product of the composition. Moreover, since the composition of the present invention exhibits high barrier properties even under high humidity, it can be suitably used for coating agents, adhesives, gas barrier materials, and the like.
Claims (16)
- 下記式（１）で表される化合物Ａと、下記式（２）で表される化合物Ｂと、
芳香環または脂環構造と２個以上のエポキシ基を有する化合物Ｃとを含有する組成物であって、組成物中のカルボキシル基に対するエポキシ基のモル比率が０．１～１．８であることを特徴とする組成物。
（式（１）において、Ｘ１は芳香環または脂環構造を表し、ｎ１およびｎ２はそれぞれ独立して０～３の整数を表す。）
（式（２）において、Ｒ１は水素原子または炭素数１～３の炭化水素基またはカルボニル基を表し、ｍ１～ｍ３はそれぞれ独立して０～３の整数を表す。） Compound A represented by the following formula (1), Compound B represented by the following formula (2),
A composition comprising an aromatic or alicyclic structure and compound C having two or more epoxy groups, wherein the molar ratio of epoxy groups to carboxyl groups in the composition is 0.1 to 1.8. A composition characterized by the above.
(In Formula (1), X 1 represents an aromatic ring or alicyclic structure, and n1 and n2 each independently represents an integer of 0 to 3.)
(In Formula (2), R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m1 to m3 each independently represents an integer of 0 to 3) - 化合物Ｃが、下記式（３）で表される構造である、請求項１に記載の組成物。
（式（３）において、Ｘ２は芳香環または脂環構造を表し、ｎ３は２～６の整数を表し、Ｒ２はそれぞれ独立して下記式（４）で表される基を表す。
（Ｙ１およびＹ３はそれぞれ独立して２価の炭化水素基または酸素原子を表し、Ｙ２は３価の炭化水素基または窒素原子を表し、ｎ４およびｎ６はそれぞれ独立して０～３の整数を表し、ｎ５は０または１であって、ｎ５が０の時ｎ７は１であって、ｎ５が１の時ｎ７は２を表す。））
The composition of Claim 1 whose compound C is a structure represented by following formula (3).
(In Formula (3), X 2 represents an aromatic ring or alicyclic structure, n3 represents an integer of 2 to 6, and R 2 independently represents a group represented by Formula (4) below.
(Y 1 and Y 3 each independently represent a divalent hydrocarbon group or an oxygen atom, Y 2 represents a trivalent hydrocarbon group or a nitrogen atom, and n4 and n6 each independently represents 0 to 3 Represents an integer, n5 is 0 or 1, n7 is 1 when n5 is 0, and n7 is 2 when n5 is 1.)
- 化合物Ｃが、脂環エポキシ化合物である、請求項１または２に記載の組成物。
The composition of Claim 1 or 2 whose compound C is an alicyclic epoxy compound.
- 前記式（１）のＸ１がベンゼン環またはナフタレン環である、請求項１～３のいずれかに記載の組成物。 The composition according to any one of claims 1 to 3, wherein X 1 in the formula (1) is a benzene ring or a naphthalene ring.
- 前記式（２）のｍ３が０である、請求項１～４のいずれかに記載の組成物。 The composition according to any one of claims 1 to 4, wherein m3 in the formula (2) is 0.
- 前記式（３）のＸ２がベンゼン環またはナフタレン環またはシクロアルカンである、請求項２～５のいずれかに記載の組成物。 The composition according to any one of claims 2 to 5, wherein X 2 in the formula (3) is a benzene ring, a naphthalene ring or a cycloalkane.
- 前記脂環エポキシ化合物の脂環エポキシ基がシクロペンテンオキシド基またはシクロヘキセンオキシド基である、請求項３～６のいずれかに記載の組成物。 The composition according to any one of claims 3 to 6, wherein the alicyclic epoxy group of the alicyclic epoxy compound is a cyclopentene oxide group or a cyclohexene oxide group.
- 前記式（１）で表される化合物Ａと、前記式（２）で表される化合物Ｂとを反応させて得られる樹脂Ｐと、芳香環または脂環構造と２個以上のエポキシ基を有する化合物Ｃとを含有することを特徴とする組成物。 A resin P obtained by reacting the compound A represented by the formula (1) with the compound B represented by the formula (2), an aromatic ring or alicyclic structure, and two or more epoxy groups. A composition comprising Compound C.
- さらに、フィラーを含有することを特徴とする請求項１～８のいずれかに記載の組成物。
The composition according to any one of claims 1 to 8, further comprising a filler.
- 請求項１～９のいずれかに記載の樹脂組成物を硬化してなる硬化物。 A cured product obtained by curing the resin composition according to any one of claims 1 to 9.
- 請求項１０に記載の硬化物層と基材とを含有する積層体。 A laminate comprising the cured product layer according to claim 10 and a substrate.
- 請求項１～９のいずれかに記載の樹脂組成物を含有することを特徴とするコーティング剤。 A coating agent comprising the resin composition according to any one of claims 1 to 9.
- 請求項１～９のいずれかに記載の組成物を含有することを特徴とする接着剤。 An adhesive comprising the composition according to any one of claims 1 to 9.
- フィルムである、請求項１０に記載の硬化物。 The cured product according to claim 10, which is a film.
- 請求項１～９のいずれかに記載の組成物を含有することを特徴とするガスバリア材料。
A gas barrier material comprising the composition according to any one of claims 1 to 9.
- 前記式（１）で表される化合物Ａと、前記式（２）で表される化合物Ｂとを反応させて樹脂Ｐを得る工程１と、
芳香環または脂環構造と２個以上のエポキシ基を有する化合物Ｃと、樹脂Ｐとを反応させて硬化物を得る工程２とを有することを特徴とする、硬化物の製造方法。 A step 1 of obtaining a resin P by reacting the compound A represented by the formula (1) with the compound B represented by the formula (2);
A process for producing a cured product, comprising: a step 2 in which a compound C having an aromatic ring or alicyclic structure and two or more epoxy groups is reacted with a resin P to obtain a cured product.
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| JP2007297604A (en) * | 2006-04-03 | 2007-11-15 | Showa Denko Kk | Thermosetting resin composition |
| JP2008045032A (en) * | 2006-08-16 | 2008-02-28 | Showa Denko Kk | Thermosetting resin composition, overcoating agent and protective film |
| WO2009011304A1 (en) * | 2007-07-18 | 2009-01-22 | Showa Denko K. K. | Heat curable resin compositon |
| JP2009280686A (en) * | 2008-05-21 | 2009-12-03 | Hitachi Chem Co Ltd | Thermosetting resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297604A (en) * | 2006-04-03 | 2007-11-15 | Showa Denko Kk | Thermosetting resin composition |
| JP2008045032A (en) * | 2006-08-16 | 2008-02-28 | Showa Denko Kk | Thermosetting resin composition, overcoating agent and protective film |
| WO2009011304A1 (en) * | 2007-07-18 | 2009-01-22 | Showa Denko K. K. | Heat curable resin compositon |
| JP2009280686A (en) * | 2008-05-21 | 2009-12-03 | Hitachi Chem Co Ltd | Thermosetting resin composition |
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