TW201927849A - Hydroxy compound, composition, cured product, and laminate - Google Patents

Abstract

The present invention provides a hydroxy compound A having a structure of general formula (1).(In formula (1), each Ar independently represents a structure having an aromatic ring having an unsubstituted or substituted group, R1 and R2 each independently represents a hydrogen atom or an alkyl group having 1-2 carbon atoms, R3 and R4 each independently represents a hydroxy group or a methyl group, n is an integer of 11-16, m is 0.5-10 of an average value of repeating numbers (where, respective repeating units present in the repeating units may be the same or different from each other).).

Description

Hydroxyl compounds, compositions, hardened materials and laminates

The present invention relates to a hydroxy compound having a specific structure, a composition having the hydroxy compound, and a cured product obtained by curing the composition. Moreover, it is about the laminated body which has this hardened | cured material layer.

Based on the reduction of CO ₂ and the increase in fuel costs, the weight reduction of automobiles and airplanes is continuing to develop. With this, the reduction in the number of point welds and the use of fiber-reinforced resins and metals are also progressing. Therefore, there is a strong demand for high performance adhesives for structural materials. In particular, in terms of heating and bonding of metals and fiber-reinforced resins with large differences in thermal expansion, the reduction of the bonding force due to the occurrence of reverse warping and the occurrence of corrugations due to the expansion and contraction interface stresses becomes a problem.

On the other hand, a laminated body of metal and plastic or a silicon wafer can also be used for cutting-edge electronic materials used in semiconductor sealing materials, insulating layers for multilayer printed circuit boards, and the like. At this time, it is necessary to use a metal with a smooth surface because of the transfer speed. However, the reduction of the anchoring effect reduces the adhesive force. This is particularly a problem for adhesives or adhesives that require a difficult metal side. Substrate.

On the other hand, most of the metal surfaces used in the industry are contaminated by organic and inorganic substances that exist in the atmosphere. Such has Organic matter and inorganic matter are deposited on the oxide layer, which further reduces the adhesion of the metal. Accordingly, there is a need for a primer that exhibits high adhesion even in a state contaminated with organic substances and the like.

For example, Patent Document 1 discloses a metal primer composition using a bisphenol A epoxy resin and a novolac epoxy resin in combination. However, these primers using general epoxy resins have not solved the problem of adhesion with respect to contaminated metal surfaces.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 2007-77358

An object of the present invention is to provide a compound that exhibits high adhesion and primer properties even on metal surfaces (especially contaminated metal surfaces).

The present invention also provides a composition containing the compound, a primer for metal, and a laminated body having the composition and a substrate as features.

The present inventors have conducted careful review and found that the aforementioned problems can be solved by providing a hydroxy compound A represented by the following formula (1). That is, the present invention provides a hydroxy compound A having a structure of the general formula (1).

In formula (1), Ar is each independently and represents a structure having an unsubstituted or substituted aromatic ring, R ₁ and R ₂ are each independently and represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₃ and R ₄ is independent and represents a hydroxyl group or a methyl group, n is an integer of 11 to 16, m is an average number of repeating units and is 0.5 to 10, (wherein each repeating unit existing in the repeating unit may be the same May also be different).

Furthermore, by providing a composition containing the hydroxy compound A, a composition containing the compound, a metal primer, and a laminated body having the composition layer and the substrate as its characteristics, Solve the aforementioned problems.

The hydroxy compound A of the present invention can exhibit high adhesion and primer properties even on metal surfaces (especially contaminated metal surfaces).

<Hydroxy compound A>

The hydroxy compound A of the present invention is a compound represented by the following formula (1).

In formula (1), Ar is each independently and represents a structure having an unsubstituted or substituted aromatic ring, R ₁ and R ₂ are each independently and represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₃ and R ₄ is independent and represents a hydroxyl group or a methyl group, n is an integer of 11 to 16, m is an average number of repeating units and is 0.5 to 10, (wherein each repeating unit existing in the repeating unit may be the same May also be different).

Among them, the hydroxyl equivalent of the hydroxy compound A is 100 to 10000 g / eq based on the viewpoint of reactivity with the adhesive layer, proper coordination to the metal surface, and flexibility, toughness, and heat resistance. Is better. In addition, the viscosity of the hydroxy compound A at 25 ° C is 100 to 20,000 Pa. The s is preferably from the viewpoint of good workability and excellent softness and adhesion of the hardened material, particularly preferably 2000 ~ 15000Pa. s.

In the general formula (1), each independently Ar system represents a structure having an unsubstituted or substituted aromatic ring. Examples of the aromatic ring system herein include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. As Ar having such a structure having an aromatic ring, it is preferable that it is a structure represented by the following formula (2).

[In formula (2), the aromatic ring may be substituted or unsubstituted, and * represents a bonding point].

In the above formula (2), from the viewpoint that the balance of the flexibility, elastic modulus, and adhesion of the cured product is excellent, it is particularly preferable that the Ar structure is as shown below.

When Ar has a substituent, examples of the substituent include an alkyl group, a halogen atom, and a hydroxyl group. An alkyl group and a hydroxyl group are preferable, and when having a hydroxyl group, it is particularly preferable because it has excellent reactivity with the adhesive layer and coordination to a metal surface.

Examples of the particularly preferable structure of Ar having a substituent include the following structures.

In the hydroxy compound A represented by the formula (1), the repeating unit n is an integer of 11 to 16, and preferably 12 to 15. When n is 11 or more, in addition to the improvement of the adhesion force, it is also possible to alleviate the anti-warp and ripple caused by the interface stress accompanying the expansion and contraction of the substrate. Moreover, when n is 16 or less, the fall of a crosslinking density can be suppressed.

<Production method of hydroxy compound A>

The method for producing the hydroxy compound A of the present invention is not particularly limited. For example, a diglycidyl ether (a1) of an aliphatic dihydroxy compound and an aromatic hydroxy compound (a2) are used in a molar ratio (a1 ) / (a2) is obtained by reacting in a range of 1 / 1.01 to 1 / 5.0.

Although the hydroxy compound A may contain an unreacted aromatic hydroxy compound (a2), the present invention can be used as it is, or the aromatic hydroxy compound (a2) can be removed and used.

The method for removing the unreacted aromatic hydroxy compound (a2) can be performed according to various methods. For example, a column chromatography separation method using a difference in polarity, a distillation fractionation method using a difference in boiling point, an alkaline aqueous solution extraction method using a difference in solubility in alkaline water, and the like can be cited. Among them, since there is no accompanying thermal deterioration, from the viewpoint of efficiency and the like, an alkaline aqueous solution extraction method is preferred. In this case, in order to dissolve the target substance, toluene, methyl isobutyl ketone, etc. may be used as the organic solvent. Among them, an organic solvent that does not mix with water, and from the viewpoint of solubility with the target, methyl isobutyl ketone is preferred. The existing rate of the unreacted aromatic hydroxy compound (a2) in the obtained hydroxy compound A is based on the viewpoint that the balance between the toughness and the flexibility of the cured product is good, and a mass ratio of 0.1 to 30 is preferred. .

The diglycidyl ether (a1) of the aliphatic dihydroxy compound is not particularly limited, and examples thereof include 1,11-undecanediol diglycidyl ether, and 1,12-twelve Alkanediol diglycidyl ether, 1,13-tridecanediol, 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecanediol diglycidyl ether, 1 , 16-hexadecanediol diglycidyl ether, 2-methyl-1,11-undecanediol diglycidyl ether, 3-methyl-1,11-undecanediol diglycidyl Glyceryl ether, 2,6,10-trimethyl-1,11-undecanediol diglycidyl ether and the like. These may contain organic chlorine impurities generated during the glycidyl etherification of a hydroxy compound, and may also contain 1-chloromethyl-2-glycidyl ether (chloromethyl), etc., as shown in the following structure. Organochlorine. These diglycidyl ether systems may be used alone or in combination of two or more.

Among these, from the viewpoint of the excellent balance between the flexibility and heat resistance of the obtained hardened product, it is preferred that a glycidyl group is connected to both ends of the alkylene chain having 12 to 14 carbon atoms via an ether group. For the compound having a structure, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, and 1,14-tetradecanediol diglycidyl ether are most preferably used.

The aromatic hydroxy compound (a2) is not particularly limited, and examples thereof include dihydroxybenzenes such as hydroquinone, resorcinol, and catechol, gallophenol, and 1,2,4-trisphenol. Triphenyls such as hydroxybenzene, 1,3,5-trihydroxybenzene, etc., Triphenylmethane type phenols such as 4,4 ', 4 "-trihydroxytriphenylmethane, 1,6-dihydroxynaphthalene , 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, etc. 1,1'-methylenebis- (2,7-naphthalene glycol), 1,1'-binaphthalene-2,2 ', 7,7'-tetraol, 1, 4-functional phenols such as 1'-oxybis- (2,7-naphthalene glycol), bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2 -Bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and 1,1-bis (4-hydroxyphenyl) -1-phenyl Bisphenols such as ethane and bis (4-hydroxyphenyl) fluorene, 2,2'-biphenol, 4,4'-biphenol, (1,1'-biphenyl) -3,4- Diol, 3,3'-dimethyl- (1,1'-biphenyl) -4,4'-diol, 3-methyl- (1,1'-biphenyl) -4,4 '-Diol, 3,3', 5,5'-tetramethylbiphenyl-2,2'-diol, 3,3 ', 5,5'-tetra Biphenyl-4,4'-diol, 5-methyl- (1,1'-biphenyl) -3,4'diol, 3'-methyl- (1,1'-biphenyl Di) -3,4'diol, 4'-methyl- (1,1'-biphenyl) -3,4'diol, biphenols, phenols and dicyclopentadiene Alicyclic structure-containing phenols, bis (2-hydroxy-1-naphthyl) methane, and bis (2-hydroxy-1) -Naphthyl) propane and other naphthols, so-called xylok-type phenol resins produced by condensation reaction of phenol with phenylene dimethyl chloride or phenylene dimethyl chloride, can be used alone or Use 2 or more types together. Furthermore, bifunctional phenol compounds having a structure in which a methyl group, a third butyl group, or a halogen atom as a substituent is substituted on the aromatic core of each of the above compounds can also be mentioned. In addition, the alicyclic structure-containing phenols and the xylok-type phenol resin system can have not only a bifunctional component but also a trifunctional component or more. The system in the present invention can be used directly or via A purification step such as a column is used to remove only the difunctional component.

Among these, bisphenols are preferred from the viewpoint that the balance between flexibility and toughness when forming a cured product is excellent, and bis (4-hydroxyphenyl) is particularly preferred from the viewpoint that the toughness imparting performance is significant. ) Methane, 2,2-bis (4-hydroxyphenyl) propane. Moreover, when the moisture resistance of hardened | cured material is emphasized, it is suitable to use the phenol which contains an alicyclic structure.

The reaction ratio between the diglycidyl ether (a1) of the aliphatic dihydroxy compound and the aromatic hydroxy compound (a2) is because the obtained compound is used as a hardener for the epoxy resin, so it must be in (a1 ) / (a2) is reacted in a range of 1 / 1.01 to 1 / 5.0 (molar ratio), and from the viewpoint that the softness and heat resistance of the obtained hardened product can be balanced and balanced, (a1) / (a2) is 1 / 1.1 to 1 / 3.0 (Molar ratio).

The reaction of the diglycidyl ether (a1) of the aliphatic dihydroxy compound with the aromatic hydroxy compound (a2) is preferably in the catalyst Perform in the presence. As the catalyst, various catalysts can be used, and examples thereof include alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide, sodium carbonate, and potassium carbonate. Phosphorus compounds such as alkali metal carbonates, triphenylphosphines, DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium, etc. chlorides, bromides, Iodide, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium, etc. chloride, bromide, quaternary ammonium salt such as iodide, triethylamine, N, N-di Tertiary amines such as methylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene, 1,4-diazabicyclo [2.2.2] octane, 2-ethyl- Imidazoles such as 4-methylimidazole and 2-phenylimidazole. These systems can also be used in combination of two or more catalysts. Among them, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred from the viewpoint that the reaction can proceed rapidly and the effect of reducing impurities is high. The use amount of these catalysts is not particularly limited, and it is preferable to use 0.0001 to 0.01 mol with respect to 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound (a2). The form of the catalyst is not particularly limited, and an aqueous solution form or a solid form may be used.

The reaction system of the diglycidyl ether (a1) of the aliphatic dihydroxy compound and the aromatic hydroxy compound (a2) can be performed without a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include methyl cyperidine, ethyl cyperidine, toluene, xylene, methyl isobutyl ketone, dimethyl sulfene, propanol, butanol, and the like. The amount of the organic solvent used is usually 50 to 300% by mass, and more preferably 100 to 250% by mass relative to the total mass of the raw materials added. These organic solvents can be used alone or in combination. For fast It is preferred that the reaction proceeds quickly, without using a solvent. On the other hand, from the viewpoint of reducing impurities in the final product, the use of dimethylsulfinium is preferred.

The reaction temperature when carrying out this reaction is usually 50 to 180 ° C, and the reaction time is usually 1 to 10 hours. From the viewpoint of reducing impurities in the final product, the reaction temperature is preferably 100 to 160 ° C. When the color of the obtained compound is large, an antioxidant or a reducing agent may be added in order to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and trivalent phosphorus atom-containing phosphite compounds. Wait. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, bisulfite, and salts thereof.

After the reaction is completed, neutralization or water washing treatment may also be performed until the pH value of the reaction mixture is 3 to 7, preferably 5 to 7. The neutralization treatment and the water washing treatment may be performed in accordance with a conventional method. For example, when a basic catalyst is used, acidic substances such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, and oxalic acid can be used as the neutralizing agent. After the neutralization or water washing treatment, if necessary, the solvent can be distilled off under reduced pressure and the product can be concentrated to obtain a compound.

As a preferable structure of the hydroxy compound A represented by this formula (1), the following structures are mentioned.

In each of the above structural formulas, R ₁₃ is a hydrogen atom and / or a methyl group, n is an integer of 11 to 16, m is an average number of repeating units, and is 0.5 to 10.

Among the above-mentioned structural formulas, from the viewpoint that the physical properties of the obtained hardened material are excellent, it is best to use the structural formulas (A-1), (A-2), (A-3), and (A-5). ), (A-8), (A-9), (A-10).

<Composition>

The composition of the present invention contains the hydroxy compound A of the present invention.

The composition of the present invention may contain a compound that reacts with the hydroxy compound A in addition to the hydroxy compound A. Examples of the compound that reacts with the hydroxy compound A include an epoxy compound and / or an isocyanate compound.

The epoxy compound that can be used in combination is not limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, Resorcinol epoxy resin, hydroquinone epoxy resin, catechol epoxy resin, dihydrogen Liquid epoxy resin such as naphthalene type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, brominated epoxy resin such as brominated phenol novolac epoxy resin, solid bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol plus Reactive epoxy resin, phenol arane type epoxy resin, phenyl ether type epoxy resin, naphthyl ether type epoxy resin, naphthol novolac type epoxy resin, naphthol arane type epoxy resin, naphthol- Novolac-type novolac epoxy resin, Naphthol-cresol novolac-type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type epoxy resin, biphenyl-modified novolac-type epoxy resin, etc. It can be used singly or in combination of two or more kinds. It is preferably selected and used according to the intended use, the physical properties of the hardened material, and the like.

In addition, as the curing agent of the epoxy compound, an amine-based compound, an acid anhydride-based compound, a fluorene-based compound, and a phenol-based compound can be used in combination.

The blending amount when an epoxy compound and an epoxy hardener are contained in the composition of the present invention is not particularly limited. From the viewpoint of good mechanical properties such as the mechanical properties of the obtained hardened product, it is preferred to be relative to epoxy. The total amount of epoxy groups in the total amount of the compound is 1 equivalent, and the total amount of the hydroxyl groups of the hydroxy compound A and the active group in the hardener is 0.7 to 1.5 equivalents.

Examples of the isocyanate compound include an aromatic polyisocyanate, an alicyclic polyisocyanate, and an aliphatic polyisocyanate.

Examples of the aromatic polyisocyanate include phenylene diisocyanate, phenylmethyl diisocyanate, dimethylphenyl diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, and triphenylmethane. Triisocyanate, naphthyl diisocyanate, polymethylene polyphenyl polyisocyanate, etc.

Examples of the alicyclic polyisocyanate include cyclohexyl diisocyanate, methyl cyclohexyl diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, and the like. .

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

These isocyanate compounds can be used alone or in combination of two or more. These systems can be used alone or in combination of two or more.

<Hardening accelerator>

For example, the composition of the present invention may contain a hardening accelerator. Various kinds of the hardening accelerator can be used, and examples thereof include urea compounds, phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. In the case of use for an adhesive agent, a urea compound is preferable from the viewpoint of excellent workability and low-temperature curing properties, and 3,4-dichlorophenyl-dimethylurea (DCMU) is particularly preferred. When used for semiconductor sealing material applications, from the viewpoints of excellent hardenability, heat resistance, electrical characteristics, and moisture resistance reliability, among the phosphorus compounds, triphenylphosphine is preferred, and tertiary amines are preferred. In particular, 1,8-diazabicyclo [5.4.0] undecene is preferred.

<Filler>

The composition of the present invention may further contain a filler. Examples of the filler include inorganic fillers and organic fillers. Examples of the inorganic filler include inorganic fine particles.

As the inorganic fine particles, for example, alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, etc.) having excellent heat resistance can be used. Crystalline silicon dioxide, ultrafine powder amorphous silicon dioxide, etc.); boron nitride, aluminum nitride, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc .; excellent thermal conductivity; Metal fillers and / or metal-coated fillers using metal monomers or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); mica, clay, kaolin, Minerals such as talc, zeolite, wollastonite, smectite, or potassium titanate, magnesium sulfate, sepiolite, xonotlite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; High refractive index barium titanate, zirconia, titanium oxide, etc .; titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, tellurium, nickel, iron, cobalt, silver, Photocatalyst metals such as molybdenum, strontium, chromium, barium, lead, etc. Metal composites, such oxides, etc .; Silicon dioxide, aluminum oxide, zirconia, magnesium oxide and other metals with excellent abrasion resistance, composites and oxides thereof; silver and copper with excellent conductivity And other metals, tin oxide, indium oxide, etc .; silicon dioxide, etc., which is excellent in insulation; titanium oxide, zinc oxide, etc., which is excellent in ultraviolet shielding.

These inorganic fine particles may be appropriately selected depending on the application, and may be used alone or in combination. Since the inorganic fine particles have various characteristics in addition to the exemplified characteristics, they may be selected in accordance with appropriate applications.

For example, when silicon dioxide is used as the inorganic fine particles, there is no particular limitation, and known silicon dioxide fine particles such as powdery silica or colloidal silica can be used. Examples of commercially available powdered silica include AEROSIL 50 and 200 manufactured by Japan Aerosil Corporation, SHIELDEX H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., and Japan Silicon Dioxide Industry Corporation. E220A, E220, FUJI SILYSIA (stock) system SYLYSIA 470, Japan plate glass (stock) system SG FLAKE and so on.

In addition, as commercially available colloidal silica, for example, a methanol silica sol manufactured by Nissan Chemical Industry Co., Ltd., IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, and ST -UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc.

The surface-modified silicon dioxide fine particles may also be used. For example, the surface-treated silicon dioxide fine particles are treated with a reactive silane coupling agent having a hydrophobic group, and the silicon dioxide fine particles are surface-treated with Compounds that modify the fine particles of silica. Examples of commercially available powdered silica modified with a compound having a (meth) acrylfluorenyl group include AEROSIL RM50 and R711 manufactured by Japan Aerosil Co., Ltd., and a compound having a (meth) acrylfluorenyl group. Examples of the commercially available modified colloidal silica include MIBK-SD manufactured by Nissan Chemical Industries, Ltd. and the like.

The shape of the silica particles is not particularly limited, and a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fibrous shape, or a non-fixed shape can be used. The primary particle size is preferably in the range of 5 to 200 nm. When it is less than 5 nm, the dispersion of the inorganic fine particles in the dispersion is insufficient, and when the diameter exceeds 200 nm, there is a possibility that the hardened material cannot maintain sufficient strength.

As the titanium oxide fine particles, not only extender pigments, but also ultraviolet light-responsive photocatalysts can be used, and for example, anatase titanium oxide, rutile titanium oxide, and brookite titanium oxide can be used. Furthermore, particles designed by a method of doping different types of elements in the crystal structure of titanium oxide to make it respond to visible light can also be used. As the element doped with titanium oxide, an anionic element such as nitrogen, sulfur, carbon, fluorine, phosphorus, and the like, and a cationic element such as chromium, iron, cobalt, and manganese are suitably used. The morphology may be a sol or a slurry in which powder is dispersed in an organic solvent or water. Examples of commercially available powdered titanium oxide fine particles include, for example, AEROSIL P-25 manufactured by Japan Aerosil Corporation, ATM-100 manufactured by TAYCA Corporation, and the like. Moreover, as a commercially available slurry-like titanium oxide fine particle, TAYCA (strand) TKD-701 etc. are mentioned, for example.

<Fibrous matrix>

The composition of the present invention may further contain a fibrous matrix. The fibrous matrix system of the present invention is not particularly limited, and it is preferably used in a fiber-reinforced resin, and examples thereof include inorganic fibers and organic fibers.

As inorganic fibers, in addition to inorganic fibers such as carbon fibers, glass fibers, boron fibers, alumina fibers, and silicon carbide fibers, Carbon fiber, activated carbon fiber, graphite fiber, glass fiber, tungsten carbide fiber, silicon carbide fiber, ceramic fiber, alumina fiber, natural fiber, mineral fiber such as basalt, boron fiber, and boron nitride Fiber, boron carbide fiber, and metal fiber. Examples of the metal fiber include aluminum fiber, copper fiber, brass fiber, stainless steel fiber, and steel fiber.

Examples of the organic fiber include polyindole, aramid, and PBO (polybenzo Azole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, polyarylate, etc. synthetic fibers of resin materials, or cellulose, pulp, cotton, wool, silk and other natural materials Regenerated fibers such as fiber, protein, peptide, alginic acid, etc.

Among them, carbon fiber and glass fiber are preferred because of their wide industrial application range. Among these, only one kind may be used, and multiple kinds may be used simultaneously.

The fibrous matrix system of the present invention may be an aggregate of fibers, and the fibers may be continuous, discontinuous, woven, or non-woven. Moreover, the fiber bundle may be a fiber bundle in which fibers are aligned in a single direction, or may be a sheet shape in which the fiber bundles are arranged. Further, the fiber assembly may have a three-dimensional shape having a thickness.

<Dispersion media>

The composition of the present invention is for the purpose of adjusting the solid content and viscosity of the composition, and a dispersion medium may be used. The dispersion medium may be any liquid medium that does not impair the effects of the present invention, and examples thereof include various organic solvents and liquid organic polymers.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), tetrahydrofuran (THF), and dihydrogen. Cyclic ethers, esters such as methyl acetate, ethyl acetate, butyl acetate, aromatics such as toluene, xylene, carbitol, cyperidine, methanol, isopropanol, butanol, Alcohols such as propylene glycol monomethyl ether can be used alone or in combination. Among them, methyl ethyl ketone is preferred in terms of volatility during coating and solvent recovery.

This liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples thereof include modified polymers containing carboxyl groups (FLOREN G-900, NC-500: Kyoeisha) , Acrylic polymer (FLOREN WK-20: Kyoeisha), amine salt of special modified phosphate (HIPLAAD ED-251: Kusumoto Chemical), modified acrylic block copolymer (DISPERBYK2000: BYK), etc.

<Resin>

Moreover, the composition system of this invention may contain resin other than the said various compound of this invention. As the resin, a known and commonly used resin may be blended as long as the effect of the present invention is not impaired, and for example, a thermosetting resin or a thermoplastic resin can be used.

A thermosetting resin is a resin that is substantially insoluble and can be changed to infusible when hardened by means such as heating, radiation, and a catalyst. Specific examples thereof include epoxy resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, and diallyl p-xylylene Ester, silicone resin, urethane resin, furan resin, ketone resin, xylene resin, thermosetting polyimide resin, benzo Resins, active ester resins, benzene resins, cyanate resins, styrene and maleic anhydride (SMA) resins, and maleimide resins. These thermosetting resins can be used singly or in combination of two or more.

Thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, and acrylonitrile-styrene ( AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, vinyl vinyl alcohol resin, cellulose acetate resin, ionic polymer , Polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polyfluorene resin , Polyphenylene sulfide resin, polyether sulfide imine resin, polyether sulfide resin, polyarylate resin, thermoplastic polyfluoride imide resin, polyfluoride sulfide resin, polyether ether ketone resin, polyketone resin, liquid crystal Polyester resin, fluororesin, syndiotactic polystyrene resin, cyclic polyolefin resin, etc. These thermoplastic resins can be used singly or in combination of two or more.

<Other Blends>

The composition system of the present invention may also have other admixtures. Examples include: catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow modifiers, coupling agents, dyes, leveling agents, rheology control Agents, UV absorbers, antioxidants, flame retardants, plasticizers, etc.

<Hardened material>

In the composition of the present invention, by using a reaction product of a diglycidyl ether of an aliphatic dihydroxy compound and an aromatic hydroxy compound, an unprecedented soft and tough hardened material can be obtained. For example, an aliphatic dicarboxylic acid such as a dimer acid or sebacic acid is used as a molecular chain extender, and a high molecular weight epoxy compound obtained by reacting the liquid bisphenol A type epoxy resin may be A hardened structure with a soft structure was obtained, but this effect was not sufficient due to the agglomeration of the ester groups.

On the other hand, in the present invention, the skeleton system generated from the aliphatic compound can function as a so-called soft segment that imparts flexibility, and thus is obtained by curing the hydroxy compound A of the present invention. The hardened system is extremely soft. On the other hand, the skeleton generated from the aromatic hydroxy compound functions as a so-called hard segment that imparts rigidity to the hydroxy compound A of the present invention, so that it can be hardened with both flexibility and toughness. Thing.

In particular, in the case of the hydroxy compound A of the present invention, the part which functions as a hard segment and the part which functions as a soft segment are bonded to each other, so that flexibility can be imparted to the structure of the hydroxy compound, and at the same time, it can exhibit excellent properties. Moisture resistance. Furthermore, the present invention is directly bonded to the aromatic nucleus through a hydroxyl group, and the toughness of the cured product is extremely excellent. That is, for example, the hydroxy compound skeleton obtained by modifying a low molecular weight liquid bisphenol A type epoxy resin with ethylene oxide or propylene oxide becomes soft, but the hydroxyl group itself has poor activity. However, the cross-linking sufficient to show toughness cannot be obtained during hardening. The hydroxy compound A of the present invention Because the hydroxyl group is directly bonded to the aromatic nucleus, the hydroxyl group becomes more active. Therefore, even if the resin itself is soft, moderate cross-linking is formed during the curing reaction, and excellent toughness is exhibited. In addition, when the hard segment is adjacent to a hydroxyl group that becomes a crosslinking point, the physical strength of the crosslinking point is increased, and the toughness is improved.

When the composition of the present invention is hardened, curing at normal temperature or heating may be performed. For curing, a known and commonly used curing catalyst or an epoxy compound or an isocyanate compound as a curing agent can be used.

When performing thermal hardening, it can be hardened by a single heating, or it can be hardened by a multi-stage heating step.

When a hardening catalyst is used, for example, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate, and acetic acid; and inorganic acids such as sodium hydroxide and potassium hydroxide Bases; Titanates such as tetraisopropyl titanate and tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5- Diazabicyclo [4.3.0] nonene-5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, mono Various compounds containing basic nitrogen atoms such as ethanolamine, imidazole, 2-ethyl-4-methyl-imidazole, 1-methylimidazole, N, N-dimethyl-4-aminopyridine (DMAP), etc. ; Is various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium salt, etc., and has chloride, bromide, carboxylate or hydroxide as relative Anions of quaternary ammonium salts; dibutyltin diacetate, dibutyltin dicaprylate, dibutyltin dilaurate, dibutyltin diethylamidopyruvate, tin octoate or tin stearate, etc. Acid salts; benzamidine peroxide, cumene hydroperoxide, bisisophenylpropyl peroxide, lauryl peroxide, di-tert-butyl peroxide, tert-butyl peroxide, methyl ethyl Organic peroxides such as ketone peroxide, tert-butyl peroxybenzoate, and the like. The catalyst can be used alone or in combination of two or more.

<Layered body>

The composition of the present invention can be laminated with a substrate to form a laminate.

As the base material of the laminated body, an inorganic material such as metal or glass, an organic material such as plastic, or wood may be appropriately used depending on the application. The shape of the laminated body is a flat plate, a sheet, or a three-dimensional structure. The three-dimensional shape is fine. Depending on the purpose, it may be an arbitrary shape having a curvature on the entire surface or a part thereof. In addition, there are no restrictions on the hardness and thickness of the substrate.

The composition of the present invention has excellent adhesion to metals and / or metal oxides, and therefore can be used favorably as a primer for metals. Examples of the metal include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and a combination thereof. Examples of the metal oxide include those metals. Single oxide and / or composite oxide. In particular, since it has excellent adhesion to iron, copper, and aluminum, it can be suitably used as a primer for iron, copper, and aluminum.

In the laminated body of the present invention, the composition layer can be directly applied to the substrate or formed by forming, or the formed one can be laminated. In the case of direct coating, the coating method is not particularly limited. Examples thereof include a spray method, a spin coating method, a dip coating method, a roll coating method, a plate coating method, a knife coating method, a blade coating method, a curtain coating method, a die coating method, a screen printing method, and an inkjet method. In the case of direct molding, examples include in-mold molding, embedded molding, vacuum molding, extrusion layer composite molding, and press molding.

<Second substrate and adhesive layer>

The laminated system of the present invention can further form a second substrate for the substrate and the composition layer. In this case, the material of the second base material is not particularly limited, and various materials listed in the aforementioned base materials can be used. Preferably, the combination of the substrate and the second substrate is any combination of metal or metal oxide and plastic.

The laminated system of the present invention may be a laminated body in which a substrate, a composition layer of the present invention, an adhesive layer, and a second substrate are sequentially laminated. The composition of the present invention works well as a primer for a metal or a metal oxide, so it is particularly good when the base material is a metal or a metal oxide. Although it does not specifically limit as an adhesive agent which forms an adhesive agent layer, if it is an epoxy resin type adhesive agent, it is preferable because adhesiveness is favorable.

<Fiber-reinforced resin>

The composition of the present invention has a fibrous matrix. When the fibrous matrix is a reinforcing fiber, the composition system containing the fibrous matrix can be used as a fiber-reinforced resin.

The method for making the composition contain a fibrous substrate is not particularly limited as long as the effect of the present invention is not impaired. Examples include kneading, coating, impregnating, injecting, and crimping the fiber substrate with the composition The method of compounding can be appropriately selected according to the fiber form and the application of the fiber-reinforced resin.

The method for molding the fiber-reinforced resin of the present invention is not particularly limited. If it is used to manufacture plate-shaped products, it is generally extruded, but it can also be pressed by plane. Other methods include extrusion molding, blow molding, compression molding, vacuum molding, and injection molding. In addition, in the case of manufacturing a film-like product, in addition to the melt extrusion method, a solution casting method can also be used. When the melt molding method is used, examples include blown film molding, cast molding, extrusion layer synthesis, and calendering. , Sheet molding, fiber molding, blow molding, injection molding, rotary molding, coating molding, etc. In the case of a resin hardened by active energy rays, various hardening methods using active energy rays can be used to produce a hardened product. In particular, when a thermosetting resin is used as a main component of the matrix resin, a molding method in which a molding material is pre-impregnated and pressurized and heated by an autoclave can be cited. In addition, examples include RTM (Resin Transfer Molding) molding, VaRTM (Vaccum assist Resin Transper molding) molding, lamination molding, and hand lamination molding.

<Prepreg>

The fiber-reinforced resin of the present invention can be formed into a state called an unhardened or semi-hardened prepreg. After the product is circulated in the state of prepreg, it can be finally hardened to form a hardened material. In the case of forming a laminated body, it is preferable because after the prepreg is formed, the other layers of the laminated layer are subjected to final hardening, thereby forming a close-knit laminated body.

The mass ratio of the composition to the fibrous substrate used at this time is not particularly limited, and it is usually prepared so that the resin portion in the prepreg becomes 20 to 60% by mass.

<Heat-resistant materials and electronic materials>

The composition of the present invention is suitable for use in heat-resistant members because of its high glass transition temperature and excellent pyrolysis resistance. In addition, since it has excellent adhesion to the substrate, it is particularly suitable for use in electronic components. In particular, it is suitable for use in semiconductor sealing materials, circuit boards, add-on films, add-on substrates, etc., or adhesives and resist materials. It is also suitable for use as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg with high heat resistance. The heat-resistant components and electronic components thus obtained are suitable for various uses. Examples include industrial machinery parts, general mechanical parts, automotive / railroad / vehicle parts, space / aerospace-related parts, electronic / electrical parts, Building materials, containers / packaging components, daily necessities, sports / leisure products, frame members for wind power generation, etc. are not limited to these.

Hereinafter, representative products will be described by way of example.

Semiconductor sealing material

Examples of the method for obtaining a semiconductor sealing material from the composition of the present invention include using an extruder, a kneader, a roller, etc. as necessary to sufficiently mix the composition, a hardening accelerator, and an inorganic filler with a compounding agent. A method of melt mixing until uniform. At this time, as the inorganic filler, fused silica is usually used, and the When using high-thermal-conductivity semiconductor sealing materials for crystals and power ICs, crystalline silicon dioxide, aluminum oxide, silicon nitride, etc., which have a higher thermal conductivity than fused silica, can be used, or fused silica, crystallinity can be used. Silicon dioxide, aluminum oxide, silicon nitride, etc. The filling rate is per 100 parts by mass of the hardening resin composition, and an inorganic filler is preferably used in a range of 30 to 95% by mass. Among them, in order to improve flame retardancy, moisture resistance, solder crack resistance, and linear expansion coefficient The reduction is more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.

2. Semiconductor device

As a semiconductor package forming method for obtaining a semiconductor device from the curable resin composition of the present invention, the above-mentioned semiconductor sealing material is formed by using a mold, a transfer molding machine, an injection molding machine, etc., and then heated at 50 to 250 ° C for 2 to 10 Hour method.

3. Printed circuit board

As a method for obtaining a printed circuit board from the composition of the present invention, the above-mentioned prepregs are laminated according to a conventional method, copper foils are appropriately overlapped, and heat-pressed at 170 to 300 ° C. under a pressure of 1 to 10 MPa. 10 minutes to 3 hours.

4. Add-on substrate

As a method of obtaining a build-up substrate from the composition of the present invention, for example, the steps are listed below. First, a spray coating method, a curtain coating method, or the like is used to coat the above-mentioned composition appropriately blended with rubber, fillers, etc. on an already formed electrode. After the circuit board is placed on the circuit board, it is cured (step 1). After that, if necessary, a predetermined through-hole portion is opened, and then the surface is treated with a roughening agent, the surface is washed with hot water to form irregularities, and a metal such as copper is plated (step 2). In response to expectations, this step is repeated in sequence, and a step of forming a resin insulation layer and a conductor layer of a predetermined circuit pattern is added in a crosswise manner (step 3). In addition, the opening of the through-hole portion is performed after the outermost surface of the resin insulating layer is formed. In addition, the add-on substrate system of the present invention can heat-compress the copper foil with resin formed by semi-hardening the resin composition on the copper foil at 170 to 300 ° C to the wiring of the formed circuit. On the substrate, the steps of forming a roughened surface and plating treatment can be omitted, and an add-on substrate can be manufactured.

5. Add-on film

As a method for obtaining a build-up film from the composition of the present invention, the organic solvent can be dried by coating the above composition on the surface of the support film (Y) belonging to the substrate, followed by heating or blowing hot air, etc. The layer (X) of the composition is formed and manufactured.

As the organic solvent used here, ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc., ethyl acetate, butyl acetate, cytarthion acetate, propylene glycol monomethyl ether acetate, card Acetates such as acetol acetate, carbitols such as cyperidine, butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethyl formaldehyde, dimethyl acetaldehyde, N- Methylpyrrolidone and the like are preferably used at a ratio of 30 to 60% by mass of nonvolatile matter.

The thickness of the layer (X) to be formed is usually greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer should preferably be 10 to 100 μm. The layer (X) of the composition of the present invention can be protected by a protective film described later. By protecting with a protective film, it is possible to prevent adhesion or damage to the surface of the resin composition layer.

Examples of the supporting film and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate, and the like. Polyester, polycarbonate, polyimide, metal foil such as release paper, copper foil, aluminum foil, etc. In addition, the support film and the protective film may be subjected to a release treatment in addition to the matting treatment and the corona treatment. The thickness of the support film is not particularly limited, and it is usually used in a range of 10 to 150 μm, preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

After the support film (Y) is laminated on a circuit board, or after an insulating layer is formed by heating and curing, the support film (Y) is peeled off. After the hardening resin composition layer constituting the build-up film is heat-hardened and the support film (Y) is peeled off, the adhesion of contaminants and the like in the hardening step can be prevented. When peeling after hardening, the support film is generally subjected to a release treatment in advance.

Using the build-up film obtained as described above, a multilayer printed circuit board can be manufactured. For example, in the case where the layer (X) is protected by a protective film, the layer (X) is laminated on the circuit substrate by a method such as vacuum lamination in a manner of directly contacting the circuit substrate after peeling them off. One or two sides. The lamination method may be a batch method or a continuous method using a roller. In addition, if necessary, the build-up film and the circuit board may be heated (preheated) as needed before lamination is performed. The lamination conditions are preferably set to a crimping temperature (laminating temperature) of 70 to 140 ° C. and a crimping pressure of 1 to 11 kgf / cm ² (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N / m ² ). Lamination was performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

6. Conductive paste

Examples of a method for obtaining a conductive paste from the composition of the present invention include a method of dispersing conductive particles in the composition. The conductive paste is a paste resin composition for circuit connection or an anisotropic conductive adhesive, depending on the type of conductive particles used.

[Example]

Next, the present invention will be described more specifically with reference to examples and comparative examples. The following "parts" and "%" are not particularly limited and are quality standards.

¹ H and ¹³ C-NMR, FD-MS spectrum, and GPC were measured under the following conditions.

¹ H-NMR: "JNM-ECA600" by JEOL RESONANCE

Magnetic field strength: 600MHz

Cumulative times: 32 times

Solvent: DMSO-d ₆

Sample concentration: 30% by mass

¹³ C-NMR: "JNM-ECA600" by JEOL RESONANCE

Magnetic field strength: 150MHz

Cumulative number: 320 times

Solvent: DMSO-d ₆

Sample concentration: 30% by mass

FD-MS: "JMS-T100GC AccuTOF" by Japan Electronics Co., Ltd.

Measuring range: m / z = 50.00 ~ 2000.00

Change rate: 25.6mA / min

Final current value: 40mA

Cathode voltage: -10kV

GPC: "HLC-8320GPC" manufactured by TOSOH Corporation

Column: "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" manufactured by TOSOH Corporation

Detector: RI (differential refractive index meter)

Measurement conditions: 40 ° C

Mobile phase: tetrahydrofuran

Flow rate: 1ml / min

Standard: "PStQuick A", "PStQuick B", "PStQuick E", "PStQuick F" made by TOSOH Corporation

Examples of the calculation method of the hydroxyl equivalent weight and the number of repeating units include calculations based on GPC molecular weight measurement, FD-MS, NMR and other appropriate instrumental analysis results.

Example 1 C12 (BPA) hydroxyl compound Ph-1

Diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthesis Co., Ltd .: epoxy equivalent 210 g / eq) 210 g (0.5 mol) and bisphenol A (hydroxy equivalent 114 g / eq) 228 g ( 1.0 mol) was added to a flask equipped with a thermometer and a stirrer, and the temperature was raised at 140 ° C for 30 minutes, and then 1 g of a 4% sodium hydroxide aqueous solution was added. Then, it heated up to 150 degreeC over 30 minutes, and also made it react at 150 degreeC for 3 hours. Thereafter, sodium phosphate was added in a neutralized amount to obtain 430 g of a hydroxy compound (Ph-1). This hydroxy compound (Ph-1) was confirmed to contain a peak corresponding to the theoretical structure of M of the general formula (1) where m is 1 and a peak of M + = 771, which was confirmed to contain the above-mentioned structural formula (A-1). Structure of hydroxy compound. The hydroxyl equivalent calculated by GPC of the hydroxy compound (Ph-1) was 330 g / eq, and the average value of m in the aforementioned structural formula (A-1) was 0.8.

Example 2 C12 (Gallaphenol) hydroxy compound Ph-2

A reaction was carried out in the same manner as in Example 1 except that 228 g (1.0 mole) of bisphenol A in Example 1 was replaced with 126 g (1.0 mole) of gallic phenol, and 330 g of a hydroxy compound Ph-2 was obtained. This hydroxy compound (Ph-2) was confirmed to contain the peak of M + = 567 corresponding to the theoretical structure in which m is 1 in the general formula (1) on the mass spectrum. Structure of hydroxy compound. Calculated by GPC of this hydroxy compound (Ph-2) The calculated hydroxyl equivalent was 121 g / eq, and the average value of m in the aforementioned structural formula (A-8) calculated from the hydroxyl equivalent was 0.8.

Example 3 C12 type (combined use of biphenol and tetramethylbiphenol) hydroxyl compound Ph-3

Except replacing 228 g (1.0 mole) of bisphenol A in Example 1 with 93 g (0.5 mole) of 4,4'-biphenol and 3,3 ', 5,5'-tetramethylbiphenyl-4 Except for 121 g (0.5 mole) of 4'-diol, a reaction was carried out in the same manner as in Example 1 to obtain 415 g of a hydroxy compound Ph-3. This hydroxy compound (Ph-3) was confirmed to contain the peaks of M + = 687, 744, and 800 corresponding to the theoretical structure in which m is 1 in the general formula (1) on the mass spectrum, and it was confirmed that the formula (A- 3) A hydroxy compound of the structure shown. The hydroxyl equivalent calculated by GPC of the hydroxyl compound (Ph-3) was 318 g / eq, and the average value of m in the aforementioned structural formula (A-3) calculated from the hydroxyl equivalent was 0.8.

Example 4 C12 (tetramethylbiphenol) hydroxy compound Ph-4

Except that 228 g (1.0 mole) of bisphenol A in Example 1 was replaced with 242 g (1.0 mole) of 3,3 ', 5,5'-tetramethylbiphenyl-4,4'-diol The reaction was carried out in the same manner as in Example 1 to obtain 458 g of a hydroxy compound Ph-4. This hydroxy compound (Ph-4) was confirmed to contain the peak of M + = 800 corresponding to the theoretical structure in which m is 1 in the general formula (1) on the mass spectrum. Structure of hydroxy compound. The hydroxyl equivalent calculated by GPC of the hydroxyl compound (Ph-4) was 342 g / eq, and the average value of m in the aforementioned structural formula (A-3) calculated from the hydroxyl equivalent was 0.8.

Example 5 C12 (2,7-dihydroxynaphthalene) hydroxy compound Ph-5

The reaction was carried out in the same manner as in Example 1 except that 228 g (1.0 mole) of bisphenol A in Example 1 was replaced with 160 g (1.0 mole) of 2,7-dihydroxynaphthalene, and 361 g of a hydroxy compound Ph-5 was obtained. . This hydroxy compound (Ph-5) was confirmed to contain a peak of M + = 635 corresponding to the theoretical structure in which m is 1 in the general formula (1) on the mass spectrum. Structure of hydroxy compound. The hydroxyl equivalent calculated by GPC of the hydroxyl compound (Ph-5) was 271 g / eq, and the average value of m in the aforementioned structural formula (A-5) calculated from the hydroxyl equivalent was 0.8.

Example 6 C12 (trisphenol methane) hydroxyl compound Ph-6

It was the same as Example 1 except that 228 g (1.0 mole) of bisphenol A in Example 1 was replaced with triphenol-based methane ("QM-100"), which is 292 g (1.0 mole). The reaction was carried out to obtain 498 g of a hydroxy compound Ph-6. This hydroxy compound (Ph-6) was confirmed to contain a peak of M + = 900 corresponding to the theoretical structure in which m is 1 in the general formula (1) on the mass spectrum, and it was confirmed that the hydroxy compound (Ph-6) contained the above-mentioned structural formula (A-9). Structure of hydroxy compound. The hydroxyl equivalent calculated by GPC of the hydroxyl compound (Ph-6) was 192 g / eq, and the average value of m in the aforementioned structural formula (A-9) calculated from the hydroxyl equivalent was 0.8.

Example 7 C12 type (pernaphthyl glycol) hydroxy compound Ph-7

Except that 228 g (1.0 mole) of bisphenol A in Example 1 was replaced with 1,1'-methylenebis- (2,7-naphthalene glycol) 332 g (1.0 mole), Example 1 was reacted in the same manner to obtain 522 g of a hydroxy compound Ph-7. This hydroxy compound (Ph-7) was confirmed to contain a peak of M + = 979 corresponding to the theoretical structure in which m is 1 in the general formula (1) on the mass spectrum, and it was confirmed that the hydroxy compound (Ph-7) contained the above-mentioned structural formula (A-10) Structure of hydroxy compound. The hydroxyl equivalent calculated by GPC of the hydroxyl compound (Ph-7) was 139 g / eq, and the average value of m in the aforementioned structural formula (A-10) calculated from the hydroxyl equivalent was 0.8.

Comparative Example 1 C6 (BPA) hydroxyl compound Ph-8

Except that 210 g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol in Example 1 was replaced with diglycidyl ether of 1,6-hexanediol (manufactured by DIC Corporation: EPICLON 726D was traded in the same manner as in Example 1 except that the epoxy equivalent was 124 g / eq) and 124 g (0.5 mol) to obtain 340 g of a hydroxy compound Ph-8. This hydroxy compound Ph-8 was confirmed to have a peak of M + = 687 on the mass spectrum. The hydroxyl equivalent calculated from the GPC of the hydroxyl compound Ph-8 was 262 g / eq.

Comparative Example 2 C9 (BPA) hydroxy compound Ph-9

Except changing 210 g (0.5 mol) of 1,12-dodecanediol diglycidyl ether in Example 1 to 1,9-nonanediol diglycidyl ether Production: Epoxy equivalent was 156 g / eq), except that 156 g (0.5 mol) was reacted in the same manner as in Example 1 to obtain 350 g of a hydroxy compound Ph-9. This hydroxy compound Ph-9 was confirmed to have a peak of M + = 729 on the mass spectrum. The hydroxyl equivalent calculated from the GPC of the hydroxy compound Ph-9 was 328 g / eq.

Formulation Example 1 Preparation of Adhesive Composition

Using a mixer ("Defoaming Rentaro ARV-200" manufactured by THINKY Co., Ltd.), 100 parts of EPICLON 850S (DIC Co., Ltd., bisphenol A type epoxy resin) as an epoxy resin and DICY as a hardener (Manufactured by Mitsubishi Chemical Corporation, "DICY7") 5.59 parts and 0.85 parts of DCMU (manufactured by DIC Corporation, B-605-IM) as a hardening accelerator were uniformly mixed to obtain an adhesive composition.

[Examples 8 to 14 and Comparative Examples 3 to 5] <Primer treatment>

A 3% ethanol solution of each hydroxy compound synthesized in Examples 1 to 7 and Comparative Examples 1 and 2 was prepared. Without degreasing, a cold-rolled steel sheet ("SPCC-SB" manufactured by TP Giken Co., Ltd.) was immersed at room temperature for 60 minutes, and then dried at room temperature for 5 hours.

<Tensile shear test>

The adhesive layer obtained in Blending Example 1 was coated on one of the two cold-rolled steel sheets ("SPCC-SB", manufactured by TP Giken Co., Ltd., 1.0 mm x 25 mm x 100 mm) subjected to primer treatment. Glass beads ("J-80" manufactured by Potters Ballotini Co., Ltd.) were added as spacers, and another aluminum plate was bonded (adhesion area: 25 mm x 12.5 mm). This was heat-hardened at 170 ° C for 30 minutes to obtain a test piece. Using this test piece, a tensile shear test was performed to evaluate adhesion. The test was performed in accordance with JIS K 6850, and the maximum point stress and the maximum point strain rate were compared.

In Comparative Example 5, a primer was not used, and a laminate was produced using only the adhesive composition.

<T-Peel Test>

The adhesive layer obtained in Blending Example 1 was coated on one of the two cold-rolled steel sheets ("SPCC-SB" manufactured by TP Technology Research Co., Ltd., 0.5 mm x 25 mm x 200 mm) that had been subjected to a primer treatment. Glass beads ("J-80" manufactured by Potters Ballotini Co., Ltd.) were added as spacers, and another aluminum plate was bonded (adhesive area: 25 mm x 150 mm). This was heat-hardened at 170 ° C for 30 minutes to obtain a test piece. Using this test piece, a T-peel test was performed to evaluate the adhesiveness. The test was performed in accordance with JIS K 6854-3, and average stresses were compared.

In Comparative Example 5, a primer was not used, and a laminate was produced using only the adhesive composition.

Industrial availability

As shown in Examples 8 to 14, the present invention has a high adhesive force in a tensile shear test and a T-peel test. In addition, in the tensile shear test, it has a high strain rate and excellent stress relaxation properties.

The hydroxy compound A of the present invention can exhibit high adhesion and primer properties even on metal surfaces (especially contaminated metal surfaces).

Claims (14)

A hydroxy compound A having the structure of the general formula (1), [In formula (1), Ar is each independently and represents a structure having an unsubstituted or substituted aromatic ring, R ₁ and R ₂ are each independently and represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₃ And R ₄ are each independent and represent a hydroxyl group or a methyl group, n is an integer of 11 to 16, m is an average number of repeating units and is 0.5 to 10, (wherein each repeating unit existing in the repeating unit may be Same or different)]. The hydroxy compound A of claim 1, wherein in the formula (1), Ar is any one of the following formula (2), [In formula (2), the aromatic ring may be substituted or unsubstituted, and * represents a bonding point]. The hydroxy compound A according to claim 1 or 2, wherein in the formula (1), Ar is a group further having a hydroxy group. A composition comprising the hydroxy compound A according to any one of claims 1 to 3. The composition according to claim 4, further comprising a compound that reacts with the hydroxy compound A. The composition according to claim 5, wherein the compound that reacts with the hydroxy compound A is an epoxy compound and / or an isocyanate compound. The composition according to any one of claims 4 to 6, further comprising a filler. A hardened material obtained by hardening the composition according to any one of claims 4 to 7. A laminated body comprising a substrate and a composition layer according to any one of claims 4 to 7. The laminated body according to claim 9, wherein the substrate is a metal or a metal oxide. If the laminated body of claim 8 or 9 is a laminated body in which a substrate, a composition layer of any of claims 4 to 7, and a second substrate are sequentially laminated, the substrate is metal or Metal oxide, and the second substrate is a plastic layer. The laminated body according to any one of claims 8 to 10 is formed by sequentially laminating a substrate, a composition layer according to any one of claims 4 to 7, an adhesive layer, and a second substrate. Laminated body, the substrate is a metal or metal oxide, and the second substrate is a plastic layer. An electronic component characterized in that it comprises a laminated body according to any one of claims 8 to 10. A primer for metal or metal oxide, characterized in that it contains a hydroxy compound A according to any one of claims 1 to 3.