KR20200100041A - Hydroxy compounds, compositions, cured products and laminates - Google Patents

Abstract

···(1)
(식(1) 중, Ar은 각각 독립해서 무치환 또는 치환기를 갖는 방향환을 갖는 구조를 나타내고,
R₁ 및 R₂은 각각 독립해서 수소 원자 또는 탄소수 1∼2의 알킬기를 나타내고,
R₃ 및 R₄은 각각 독립해서 수산기 또는 메틸기를 나타내고,
n은 11∼16의 정수이고, m은 반복수의 평균값으로 0.5∼10이다.
(단, 반복 단위 중에 존재하는 각 반복 단위는 각각 동일해도 되고 달라도 상관없다))The present invention provides a hydroxy compound A having a structure of general formula (1).

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

Description

Hydroxy compounds, compositions, cured products 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. Further, it relates to a laminate having the cured product layer.

Weight reduction of automobiles and airplanes is gradually progressing due to reduction of CO ₂ and improvement of fuel economy, and accordingly, reduction of the number of spot welding and the combination of fiber-reinforced resin and metal are in progress. There is a strong demand for high performance. In particular, in heat bonding between a metal having a large difference in thermal expansion and a fiber-reinforced resin, a problem is a decrease in the adhesive force due to the occurrence of warpage or wave shape due to interfacial stress accompanying expansion and contraction.

On the other hand, laminates of metal, plastic, and silicon chips are also used for cutting-edge electronic materials used for semiconductor encapsulation materials and insulating layers for multilayer printed circuit boards. At this time, it is necessary to use a metal with a smooth surface due to the relationship of the transmission speed, etc., but the decrease in the anchoring effect is a serious problem, and in particular, an adhesive on the metal side that is difficult to bond or an adhesive primer is required. .

On the other hand, the metal surface used for industrial purposes is often contaminated by organic substances or inorganic substances existing in the air. These organic substances or inorganic substances are deposited on the oxide layer, further reducing the adhesion of the metal. Therefore, there is a demand for a primer that exhibits high adhesiveness even in a state contaminated with organic substances or the like.

For example, in Patent Document 1, a primer composition for metals using a bisphenol A type epoxy resin and a novolac type epoxy resin in combination is disclosed. However, the problem of adhesion to a contaminated metal surface is not solved by the primers using such ordinary epoxy resins.

Japanese Unexamined Patent Publication No. 2007-77358

An object of the present invention is to provide a compound that exhibits high adhesion and primer properties even on a metal surface, particularly a contaminated metal surface.

Further, it is to provide a composition containing the compound, a primer for metal, and a laminate comprising the composition layer and the substrate.

As a result of intensive examination, the present inventors found out that the above problem can be solved by providing the hydroxy compound A represented by the following formula (1). That is, the present invention is to provide a hydroxy compound A having a structure of general formula (1).

···(One)

In formula (1), Ar each independently represents a structure having an unsubstituted or substituted aromatic ring,

R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,

R ₃ and R ₄ each independently represent a hydroxyl group or a methyl group,

n is an integer of 11 to 16, and m is an average value of the number of repetitions, and is 0.5 to 10.

(However, each repeating unit present in the repeating unit may be the same or different.)

In addition, by providing a composition containing the hydroxy compound A, a composition containing the compound, and a primer for metal, and a laminate characterized by having the composition layer and the substrate, the above subject is solved. Solve.

The hydroxy compound A of the present invention can exhibit high adhesion and primer properties even on a metal surface, particularly a contaminated metal surface.

<Hydroxy compound A> The hydroxy compound A of this invention is a compound represented by following formula (1).

···(One)

(In formula (1), Ar each independently represents a structure having an unsubstituted or substituted aromatic ring,

R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,

R ₃ and R ₄ each independently represent a hydroxyl group or a methyl group,

n is an integer of 11 to 16, and m is an average value of the number of repetitions, and is 0.5 to 10.

(However, each repeating unit present in the repeating unit may be the same or different, respectively).

Among these, those having a hydroxyl equivalent of the hydroxy compound A of 100 to 10000 g/eq are preferable from the viewpoint of reactivity with the adhesive layer, suitable coordination to the metal surface, and both flexible toughness and heat resistance. In addition, it is preferable that the viscosity of the hydroxy compound A at 25°C is 100 to 20000 Pa·s, from the viewpoint of good workability and excellent flexibility and adhesion of the cured product, particularly 2,000 to 15,000 Pa·s. desirable.

In the general formula (1), each independently Ar represents a structure having an unsubstituted or substituted aromatic ring. The aromatic ring herein includes, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Ar, which is a structure having these aromatic rings, preferably shows a structure represented by the following formula (2).

···(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 of excellent balance of flexibility, elastic modulus, and adhesiveness of the cured product, the structure of Ar is particularly preferably the following.

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

The following structures are mentioned as a particularly preferable structure as Ar having a substituent.

In the hydroxy compound A represented by the above formula 1, the repeating unit n is an integer of 11 to 16, and preferably 12 to 15. When n is 11 or more, adhesive strength is improved, and warpage or wavy shape due to interfacial stress accompanying expansion and contraction of the substrate can be alleviated. In addition, when n is 16 or less, a decrease in 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, but for example, the diglycidyl ether (a1) of the aliphatic dihydroxy compound and the aromatic hydroxy compound (a2) are mixed in a molar ratio ( It is obtained by reacting in the range of 1/1.01 to 1/5.0 of a1)/(a2).

The unreacted aromatic hydroxy compound (a2) is contained in the hydroxy compound A, but in the present invention, it may be used as it is, or may be used after removing the aromatic hydroxy compound (a2).

As a method for removing the unreacted aromatic hydroxy compound (a2), it can be carried out in accordance with 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 water extraction method using a difference in solubility in alkaline water, and the like may be mentioned. Among them, since it does not involve heat deterioration, the alkaline water extraction method is preferable in terms of efficiency, etc., and the organic solvent used to dissolve the target substance at this time can be used as long as it is not mixed with water such as toluene or methyl isobutyl ketone. , Methyl isobutyl ketone is preferable from the viewpoint of solubility with the target substance. It is preferable that the abundance of the unreacted aromatic hydroxy compound (a2) in the resulting hydroxy compound A is 0.1 to 30 in terms of mass %, from the viewpoint of a good balance between toughness and flexibility of the cured product.

The diglycidyl ether (a1) of the aliphatic dihydroxy compound is not particularly limited, and for example, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether , 1,13-tridecanediol, 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecandiol diglycidyl ether, 1,16-hexadecanediol diglycidyl ether, 2- Methyl-1,11-undecanediol diglycidyl ether, 3-methyl-1,11-undecanediol diglycidyl ether, 2,6,10-trimethyl-1,11-undecanediol diglycidyl ether, etc. Can be mentioned. These may contain organic chlorine impurities generated in the glycidyl etherification of the hydroxy compound, and organic chlorine such as 1-chloromethyl-2-glycidyl ether (chloromethyl form) represented by the following structure It may contain. These diglycidyl ethers may be used alone or in combination of two or more.

...Chloromethyl form

Among these, a compound having a structure in which a glycidyl group is connected via an ether group at both ends of an alkylene chain having 12 to 14 carbon atoms is preferable from the viewpoint of excellent balance of flexibility and heat resistance of the resulting cured product, and 1,12-dodecanedi It is most preferable to use old diglycidyl ether, 1,13-tridecanediol, and 1,14-tetradecanediol diglycidyl ether.

The aromatic hydroxy compound (a2) is not particularly limited, and examples include dihydroxybenzenes such as hydroquinone, resorcin, and catechol, pyrogallol, and 1,2,4-trihydroxybenzene , Trihydroxybenzenes such as 1,3,5-trihydroxybenzene, triphenylmethane-type phenols such as 4,4',4"-trihydroxytriphenylmethane, 1,6-dihydroxynaphthalene, Dihydroxy, such as 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene 1,1'-methylenebis-(2,7-naphthalenediol), 1,1'-binaphthalene-2,2',7,7'-tetra obtained by coupling reaction of naphthalenes and dihydroxynaphthalenes Tetrafunctional phenols such as ol, 1,1'-oxybis-(2,7-naphthalenediol), 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-phenylethane, And bisphenols such as bis(4-hydroxyphenyl)sulfone, 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'-tetramethylbiphenyl-4,4'-diol, 5-methyl-(1,1'-biphenyl)- Ratio of 3,4' diol, 3'-methyl-(1,1'-biphenyl)-3,4' diol, 4'-methyl-(1,1'-biphenyl)-3,4' diol, etc. Phenols containing alicyclic structures such as phenols, polyadditions of phenol and dicyclopentadiene, and polyadditions of phenol and terpene compounds, bis(2-hydroxy-1-naphthyl)methane, and bis( Naphthols such as 2-hydroxy-1-naphthyl)propane, and a so-called xyloxy phenol resin, which is a condensation reaction product of phenol and phenylene dimethyl chloride or biphenylene dimethyl chloride, may be used alone, or two types You may use the above in combination. In addition, as a substituent in the aromatic nucleus of each of the above compounds, methyl group, t-butyl A group or a difunctional phenol compound having a structure substituted with a halogen atom may also be mentioned. In addition, the alicyclic structure-containing phenols and the xylox-type phenol resin may be present at the same time as not only a bifunctional component, but also a component having a trifunctional or higher function. , You may take out and use only the bifunctional component.

Among these, bisphenols are preferred from the viewpoint of excellent balance of flexibility and toughness when used as a cured product. In particular, bis(4-hydroxyphenyl)methane and 2,2-bis(4) from the viewpoint of remarkable performance for imparting toughness. -Hydroxyphenyl)propane is preferred. In addition, when placing importance on the moisture resistance of the cured product, it is preferable to use phenols containing an alicyclic structure.

The reaction ratio of the aliphatic dihydroxy compound to the diglycidyl ether (a1) and the aromatic hydroxy compound (a2) is, in order to use the obtained compound as a curing agent for the epoxy resin, (a1)/(a2 ) Is required to react in a range of 1/1.01 to 1/5.0 (molar ratio), and (a1)/(a2) is 1/1.1 to 1/ from the point that the obtained cured product has a good balance of flexibility and heat resistance. It is preferably 3.0 (molar ratio).

It is preferable that the reaction between the diglycidyl ether (a1) of the aliphatic dihydroxy compound and the aromatic hydroxy compound (a2) is performed in the presence of a catalyst. Various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, phosphorus such as triphenylphosphine Chlorides such as compounds, DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium, bromide, iodide, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyl Chlorides such as tributylphosphonium, quaternary ammonium salts such as bromide and iodide, triethylamine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undecene, 1,4- Tertiary amines such as diazabicyclo[2.2.2]octane, imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole, and the like. These may use 2 or more types of catalyst together. Among them, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because the reaction proceeds rapidly and the effect of reducing the amount of impurities is high. Although the amount of these catalysts to be used is not particularly limited, it is preferable to use 0.0001 to 0.01 moles per mole of the phenolic hydroxyl groups of the aromatic hydroxy compound (a2). The form of these catalysts is also not particularly limited, and may be used in the form of an aqueous solution, or may be used in a solid form.

Further, the reaction of the aliphatic dihydroxy compound with the diglycidyl ether (a1) and the aromatic hydroxy compound (a2) can be carried out in a non-solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, and butyl alcohol. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the added raw material. These organic solvents can be used alone or in combination of several types. In order to carry out the reaction quickly, a solvent-free is preferred, while the use of dimethyl sulfoxide is preferred from the viewpoint of reducing impurities in the final product.

The reaction temperature when performing the above reaction is usually 50 to 180°C, and the reaction time is usually 1 to 10 hours. The reaction temperature is preferably 100 to 160°C from the viewpoint of reducing impurities in the final product. Moreover, when the coloring of the obtained compound is large, in order to suppress it, you may add an antioxidant or a reducing agent. Although it does not specifically limit as an antioxidant, For example, a hindered phenol type compound, such as a 2,6-dialkylphenol derivative, a divalent sulfur type compound, and a phosphorus acid ester type compound containing a trivalent phosphorus atom, etc. are mentioned. Although it does not specifically limit as a reducing agent, For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, these salts, etc. are mentioned.

After completion of the reaction, neutralization or washing with water may be performed until the pH value of the reaction mixture becomes 3 to 7, preferably 5 to 7. Neutralization treatment or water washing treatment may be performed according to an ordinary method. For example, when a basic catalyst is used, an acidic substance such as hydrochloric acid, monosodium hydrogen phosphate, p-toluenesulfonic acid, or oxalic acid can be used as the neutralizing agent. After neutralization or washing with water, if necessary, the solvent is distilled off under reduced pressure heating and the product is concentrated to obtain a compound.

As a preferable structure of the hydroxy compound A represented by the said 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 value of repetition, and is 0.5 to 10.

Among the above structural formulas, since the physical property balance of the obtained cured product is excellent, the structural formulas (A-1), (A-2), (A-3), (A-5), (A-8), (A- It is most preferable to use those represented by 9) and (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, in addition to the hydroxy compound A, a compound that reacts with the hydroxy compound A. Examples of the compound reacting 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 at all, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroqui Liquid epoxy resins such as non-type epoxy resins, catechol-type epoxy resins, dihydroxynaphthalene-type epoxy resins, biphenyl-type epoxy resins, and tetramethylbiphenyl-type epoxy resins, and brominated epoxy resins such as bromophenol novolak-type epoxy resins, Solid bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type Epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, Aromatic hydrocarbon formaldehyde resin-modified phenol resin-type epoxy resin, biphenyl-modified novolak-type epoxy resin, etc., may be used alone or in combination of two or more, and various selections depending on the intended use or physical properties of the cured product It is preferable to use it.

Further, as a curing agent for the epoxy compound, an amine compound, an acid anhydride compound, an amide compound, and a phenol compound may be used in combination.

The amount of the epoxy compound and the epoxy curing agent contained in the composition of the present invention is not particularly limited, but since the mechanical properties of the resulting cured product are good, based on the total amount of epoxy groups in the total amount of the epoxy compound, the hydroxy compound The total amount of the hydroxyl group of A and the active group in the curing agent is preferably 0.7 to 1.5 equivalents.

As an isocyanate compound, an aromatic polyisocyanate, an alicyclic polyisocyanate, an aliphatic polyisocyanate, etc. are mentioned, for example.

As aromatic polyisocyanate, for example, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl poly Isocyanate etc. are mentioned.

Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

As an aliphatic polyisocyanate, methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, etc. are mentioned, for example.

These isocyanate compounds may be used alone or in combination of two or more. These may be used individually or may be used by mixing two or more types.

<hardening accelerator>

For example, the composition of the present invention may contain a curing accelerator. Various types of curing accelerators can be used, but examples thereof include urea compounds, phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In the case of using as an adhesive, a urea compound, particularly 3,4-dichlorophenyl-dimethylurea (DCMU), is preferable from the viewpoint of excellent workability and low-temperature curing properties. When used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical properties, moisture resistance, and the like. Therefore, triphenylphosphine is triphenylphosphine for phosphorus compounds, and 1,8-diazabicyclo-[5.4.0] ]-Undecene is preferred.

<filler>

The composition of the present invention may further contain a filler. As a filler, an inorganic filler and an organic filler are mentioned. As an inorganic filler, inorganic fine particles are mentioned, for example.

Examples of the inorganic fine particles include alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultra-fine amorphous silica, etc.), etc., as inorganic fine particles having excellent heat resistance; Examples of excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, and the like; Metal fillers and/or metal-coated fillers using a single metal or an alloy (for example, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.) ; Examples of excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, and smectite, and potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, Zinc oxide, magnesium hydroxide; Examples of the high refractive index include barium titanate, zirconia oxide, and titanium oxide; Photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, terium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium and lead , Composites of the metals, oxides thereof, and the like; Examples of excellent abrasion resistance include metals such as silica, alumina, zirconia, and magnesium oxide, and composites and oxides thereof; Examples of excellent conductivity include metals such as silver and copper, tin oxide, and indium oxide; Examples of excellent insulating properties include silica; Examples of excellent ultraviolet shielding are titanium oxide and zinc oxide.

These inorganic fine particles may be appropriately selected depending on the application, may be used alone, or may be used in combination of multiple types. In addition, since the inorganic fine particles have various properties in addition to the exemplified properties, they can be selected according to the intended use.

For example, when silica is used as the inorganic fine particles, there is no particular limitation, and known fine silica fine particles such as powdered silica or colloidal silica can be used. As commercially available powdery silica fine particles, for example, Nippon Aerosil Co., Ltd. Aerozil 50, 200, Asahi Glass Co., Ltd. Sildex H31, H32, H51, H52, H121, H122, Nippon Silica High School Co., Ltd. E220A, E220, Fuji Sirisia Co., Ltd. SYLYSIA470, Nippon Ita Glass Co., Ltd. SG flake, etc. are mentioned.

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

Surface-modified silica fine particles may be used, and examples thereof include those obtained by surface-treating the silica fine particles with a reactive silane coupling agent having a hydrophobic group or a compound having a (meth)acryloyl group. As commercially available powdery silica modified with a compound having a (meth)acryloyl group, a commercially available powder modified with a compound having a (meth)acryloyl group, such as aerozyl RM50 and R711 manufactured by Nippon Aerosil Co., Ltd. Nissan Chemical Industries, Ltd. MIBK-SD etc. are mentioned as colloidal silica.

The shape of the silica fine particles is not particularly limited, and a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an irregular shape may be used. Further, the primary particle diameter is preferably in the range of 5 to 200 nm. If it is less than 5 nm, dispersion of the inorganic fine particles in the dispersion becomes insufficient, and at a diameter exceeding 200 nm, there is a fear that sufficient strength of the cured product cannot be maintained.

As the titanium oxide fine particles, not only an extender pigment but also an ultraviolet light-responsive photocatalyst can be used, and for example, anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, and the like can be used. Further, it can also be used for particles designed to respond to visible light by doping a different element in the crystal structure of titanium oxide. As an element to be doped with titanium oxide, anionic elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, and cationic elements such as chromium, iron, cobalt, and manganese are suitably used. In addition, as a form, a powder, a sol or a slurry dispersed in an organic solvent or in water can be used. Examples of commercially available powdery titanium oxide fine particles include Nippon Aerozil Co., Ltd. Aerozil P-25, Teika Co., Ltd. ATM-100, and the like. Moreover, as a commercially available slurry-like titanium oxide fine particle, Teika Corporation TKD-701 etc. are mentioned, for example.

<Fibrous substrate>

The composition of the present invention may further contain a fibrous substrate. The fibrous substrate of the present invention is not particularly limited, but it is preferably used for a fiber-reinforced resin, and inorganic fibers and organic fibers are exemplified.

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

As organic fibers, synthetic made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylenebenzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate And natural fibers such as fibers, cellulose, pulp, cotton, wool, and nuts, and regenerated fibers such as proteins, polypeptides, and alginic acid.

Among them, carbon fibers and glass fibers are preferable because they have a wide range of industrial applications. Among these, only one type may be used, and multiple types may be used simultaneously.

The fibrous substrate of the present invention may be an aggregate of fibers, may be continuous or discontinuous, and may be a woven fabric or a nonwoven fabric. Further, it may be a fiber bundle in which the fibers are arranged in one direction, or a sheet shape in which the fiber bundles are arranged. Further, it may be a three-dimensional shape in which the aggregate of fibers has a thickness.

<Dispersion medium>

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

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), cyclic ethers such as tetrahydrofuran (THF) and dioxolane, methyl acetate, ethyl acetate, Esters such as butyl acetate, aromatics such as toluene and xylene, alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether, and these can be used alone or in combination. In particular, methyl ethyl ketone is preferable from the viewpoint of volatility during coating and solvent recovery.

The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction. For example, a carboxyl group-containing polymer modified product (Floren G-900, NC-500: Kyoeisha), an acrylic polymer (Florene WK- 20: Kyoeisha), an amine salt of a special modified phosphate ester (HIPLAAD ED-251: Kusumoto Kasei), a modified acrylic block copolymer (DISPERBYK2000; Big Chemie), and the like.

<resin>

Further, the composition of the present invention may have resins other than the aforementioned various compounds of the present 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.

The thermosetting resin is a resin having properties that can be changed substantially insoluble and infusible when cured by heating or by means such as radiation or catalyst. Specific examples thereof include epoxy resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, silicone resin, urethane resin, furan resin, ketone resin. , Xylene resin, thermosetting polyimide resin, benzoxazine resin, active ester resin, aniline resin, cyanate ester resin, styrene maleic anhydride (SMA) resin, and maleimide resin. These thermosetting resins can be used alone or in combination of two or more.

The 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, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, Polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, Polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin , Polyamideimide resin, polyether ether ketone resin, polyketone resin, liquid crystal polyester resin, fluorine resin, syndiotactic polystyrene resin, cyclic polyolefin resin, and the like. These thermoplastic resins can be used alone or in combination of two or more.

<Other formulations>

The composition of the present invention may have other formulations. For example, catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, Flame retardants, plasticizers, etc. are mentioned.

<hardened cargo>

In the composition of the present invention, by applying a reaction product of a diglycidyl ether of an aliphatic dihydroxy compound and an aromatic hydroxy compound, it becomes possible to obtain a flexible and tough cured product that is not conventional. For example, a high molecular weight epoxy compound obtained by reacting the above liquid bisphenol A epoxy resin with an aliphatic dicarboxylic acid such as dimer acid or sebacic acid as a molecular chain extender gives a cured product of a flexible structure, but The effect is not sufficient by aggregation.

On the other hand, in the present invention, since the skeleton generated from the aliphatic compound functions as a so-called soft segment that imparts flexibility, the cured product obtained by curing the hydroxy compound A of the present invention is extremely flexible. On the other hand, since 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, a cured product having both flexibility and toughness can be provided.

In particular, in the case of the hydroxy compound A of the present invention, by bonding a portion functioning as a hard segment and a portion functioning as a soft segment, it is possible to impart flexibility to the structure of the hydroxy compound and exhibit excellent moisture resistance. . Further, in the present invention, the toughness of the cured product is extremely excellent because the hydroxy group is directly bonded to the aromatic nucleus. That is, for example, the hydroxy compound skeleton itself obtained by modifying a liquid bisphenol A type epoxy resin of a low molecular weight type with ethylene oxide or propylene oxide becomes flexible, but the activity of the hydroxy group itself decreases, and toughness is expressed during curing. Although sufficient crosslinking could not be obtained, the hydroxy compound A of the present invention increases the activity of the hydroxy group by directly binding the hydroxy group to the aromatic nucleus, and therefore forms an appropriate crosslink during the curing reaction, regardless of the flexibility of the resin itself. Thus, excellent toughness is expressed. Further, when the hard segment is adjacent to the hydroxy group serving as the crosslinking point, the physical strength at the crosslinking point increases, thereby improving the toughness.

In the case of curing the composition of the present invention, curing by room temperature or heating may be performed. When curing, an epoxy compound or an isocyanate compound may be used as a known and commonly used curing catalyst or a curing agent.

In the case of thermal curing, it may be cured with one heating or may be cured through a multi-stage heating process.

In the case of using a curing catalyst, 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; Inorganic bases such as sodium hydroxide or potassium hydroxide; Titanic acid esters 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, monoethanolamine, imidazole, 2-ethyl-4-methyl-imidazole, 1-methylimidazole, N,N-dimethyl-4- Compounds containing various basic nitrogen atoms such as aminopyridine (DMAP); Various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt, and dilauryldimethylammonium salt, and quaternary ammonium salts having chloride, bromide, carboxylate, or hydroxide as counter anions; Tin carboxylates such as dibutyl tin diacetate, dibutyl tin dioctoate, dibutyl tin dilaurate, dibutyl tin diacetylacetonate, tin octylate or tin stearate; Use peroxides such as benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxane, methyl ethyl ketone peroxide, and t-butyl perbenzoate. I can. The catalyst may be used alone or in combination of two or more.

<Laminate>

The composition of the present invention can be formed into a laminate by laminating with a substrate.

As the base material of the laminate, an inorganic material such as metal or glass, or an organic material such as plastic or wood may be used in a timely manner depending on the application, and the shape of the laminate may also have a flat plate, sheet shape, or a three-dimensional structure. It does not matter if it is a three-dimensional image. Any shape according to the purpose, such as having a curvature on the entire surface or in part, may be used. In addition, there are no restrictions on the hardness and thickness of the substrate.

Since the composition of the present invention has particularly high adhesion to metals and/or metal oxides, it can be particularly favorably used as a primer for metals. Examples of metals include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and materials in which these metals are combined, and as metal oxides, single oxides and/or composites of these metals Oxides are mentioned. In particular, since it has excellent adhesion to iron, copper and aluminum, it can be favorably used as a primer for iron, copper and aluminum.

In the laminate of the present invention, the composition layer may be formed by direct coating or molding on the substrate, or may be laminated in advance. In the case of direct coating, the coating method is not particularly limited, and the spray method, spin coat method, dip method, roll coat method, blade coat method, doctor roll method, doctor blade method, curtain coat method, slit coat method, screen printing method, inkjet And the law. In the case of direct molding, in-mold molding, insert molding, vacuum molding, extrusion laminate molding, press molding, and the like are mentioned.

<Second substrate and adhesive layer>

The laminate of the present invention may further form a second substrate with respect to the substrate and the composition layer. At this time, the material of the second substrate is not particularly limited, and can be used for various materials contained in the substrate. Preferably, the combination of the base material and the second base material is a case where the combination of metal or metal oxide and plastic is any one.

Further, the laminate of the present invention may be a laminate obtained by laminating a substrate, a composition layer of the present invention, an adhesive layer, and a second substrate in this order. Since the composition of the present invention works well as a primer for a metal or metal oxide, it is particularly good when the substrate is a metal or metal oxide. The adhesive for forming the adhesive layer is not particularly limited, but an epoxy resin-based adhesive is preferable because adhesiveness is good.

<Fiber Reinforced Resin>

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

The method of containing the fibrous substrate in the composition is not particularly limited as long as the effect of the present invention is not impaired, and the fibrous substrate and the composition are combined by a method such as kneading, coating, impregnation, injection, or compression. The method is mentioned, and it can be selected in a timely manner according to the shape of the fiber and the application of the fiber-reinforced resin.

The method for molding the fiber-reinforced resin of the present invention is not particularly limited. In the case of manufacturing a plate-shaped product, the extrusion molding method is common, but it is also possible by a flat press. In addition to this, it is possible to use an extrusion molding method, a blow molding method, a compression molding method, a vacuum molding method, an injection molding method, or the like. In addition, if it is to manufacture a film-like product, in addition to the melt extrusion method, a solution cast method can be used. If the melt molding method is used, inflation film molding, cast molding, extrusion lamination molding, calender molding, sheet molding, fiber molding, blown Molding, injection molding, rotational molding, and coating molding. Further, in the case of a resin cured with an active energy ray, a cured product can be produced using various curing methods using an active energy ray. In particular, in the case of using a thermosetting resin as the main component of the matrix resin, a molding method in which a molding material is prepreged and heated by press or autoclave is mentioned.In addition, RTM (Resin Transfer Molding) molding, VaRTM (Vaccum assist Resin Transfer Molding) molding, lamination molding, and hand layup molding.

<Prepreg>

The fiber-reinforced resin of the present invention can form a state called uncured or semi-cured prepreg. After passing the product in the state of a prepreg, final curing may be performed to form a cured product. In the case of forming a layered product, it is preferable to form a layered product in which each layer is in close contact by forming a prepreg and then laminating other layers and then performing final curing.

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

<Heat-resistant materials and electronic materials>

The composition of the present invention can be suitably used for a heat-resistant member because the cured product has a high glass transition temperature and excellent thermal decomposition resistance. In addition, since it is excellent in adhesion to the substrate, it can be particularly suitably used for an electronic member. In particular, it can be suitably used for semiconductor encapsulants, circuit boards, build-up films, build-up substrates, etc., as well as adhesives and resist materials. Further, it can be suitably used for a matrix resin of a fiber-reinforced resin, and is particularly suitable as a high heat-resistant prepreg. The heat-resistant member and the electronic member obtained in this way can be suitably used for various applications, and for example, industrial machinery parts, general mechanical parts, parts such as automobiles, railroads, vehicles, aerospace related parts, electronic and electrical parts, Building materials, containers and packaging members, daily necessities, sports and leisure articles, and casing members for wind power generation may be mentioned, but are not limited thereto.

Hereinafter, a representative product will be described by way of example.

1. Semiconductor encapsulation material

As a method of obtaining a semiconductor encapsulation material from the composition of the present invention, a method of sufficiently melt-mixing the composition and a blending agent such as a curing accelerator and an inorganic filler, if necessary, using an extruder, a kneader, or a roll until uniform Can be mentioned. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, high fillers such as crystalline silica, alumina, silicon nitride, etc., which have higher thermal conductivity than fused silica, or Fused silica, crystalline silica, alumina, silicon nitride, or the like may be used. The filling ratio is preferably used in the range of 30 to 95% by mass of the inorganic filler per 100 parts by mass of the curable resin composition.In particular, in order to improve flame retardancy, moisture resistance, solder crack resistance, and decrease the linear expansion coefficient, It is more preferable that it is 70 mass parts or more, and it is still more preferable that it is 80 mass parts or more.

2. Semiconductor device

In the semiconductor package molding for obtaining a semiconductor device from the curable resin composition of the present invention, the semiconductor encapsulating material is molded using a mold or a transfer molding machine, an injection molding machine, etc., and further heated at 50 to 250°C for 2 to 10 hours. How to do it.

3. Printed circuit board

As a method of obtaining a printed circuit board from the composition of the present invention, the prepreg is laminated by a conventional method, and an appropriate copper foil is overlapped, and under pressure of 1 to 10 MPa at 170 to 300°C for 10 minutes to 3 hours. , A method of heat-pressing.

4. Build-up board

As a method of obtaining a build-up substrate from the composition of the present invention, the following steps may be mentioned, for example. First, a step of curing after applying the composition in which a rubber, a filler, or the like is appropriately blended, to a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, or the like (Step 1). After that, if necessary, a predetermined through-hole is drilled, and then treated with a roughening agent, the surface is washed to form irregularities, and metal such as copper is plated. (Step 2). A step of sequentially repeating such an operation as desired, and alternately building up and forming a resin insulating layer and a conductor layer of a predetermined circuit pattern (Step 3). In addition, drilling of the through-hole portion is performed after formation of the outermost resin insulating layer. In addition, in the build-up substrate of the present invention, a roughened surface is formed and a plating treatment is performed by heat-pressing a copper foil with a resin obtained by radiating the resin composition on a copper foil at 170 to 300°C on a circuit-formed wiring board. It is also possible to omit the process and manufacture a build-up substrate.

5. Build-up film

As a method of obtaining a build-up film from the composition of the present invention, the composition is applied to the surface of the support film (Y) as a substrate, and the organic solvent is further dried by heating or hot air spraying, and the layer (X) of the composition It can be produced by forming.

Examples of the organic solvent used herein include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and acetic acid esters such as carbitol acetate. , Carbitols such as cellosolve and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and non-volatile content 30 It is preferable to use it in a ratio of -60 mass%.

The thickness of the formed layer (X) is usually equal to or larger 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 is preferably 10 to 100 µm. Moreover, the layer (X) of the said composition in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent adhesion and scratches of dust or the like on the surface of the resin composition layer.

The above supporting film and protective film are polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as ``PET''), polyester such as polyethylene naphthalate, polycarbonate, and polyimide. And also metal foils such as release paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to mold release treatment in addition to the mad treatment and corona treatment. Although the thickness of the supporting film is not particularly limited, it is usually 10 to 150 µm, and is preferably used in the range of 25 to 50 µm. In addition, the thickness of the protective film is preferably 1 to 40 µm.

The above-described support film (Y) is peeled off after laminating on a circuit board or after forming an insulating layer by heat curing. When the support film (Y) is peeled after the curable resin composition layer constituting the build-up film is heat-cured, adhesion of dust or the like in the curing step can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

A multilayer printed circuit board can be manufactured using the build-up film obtained as described above. For example, if the layer (X) is protected by a protective film, after peeling them, the layer (X) is laminated on one or both sides of the circuit board in direct contact with the circuit board, for example by a vacuum lamination method. do. The method of laminating may be a batch type or continuous roll type. Further, if necessary, the build-up film and the circuit board may be heated (preheated) as necessary before performing lamination. As for the conditions of the lamination, it is preferable that the pressing temperature (lamination temperature) be 70 to 140°C, the pressing pressure is preferably 1 to 11 kgf/cm 2 (9.8×10 ^{4 to} 107.9×10 ⁴ N/m 2 ), It is preferable to laminate the air pressure under reduced pressure of 20 mmHg (26.7 hPa) or less.

6. Conductive paste

As a method of obtaining a conductive paste from the composition of the present invention, for example, a method of dispersing electroconductive particles in the composition may be mentioned. The said conductive paste can be made into a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the kind of electroconductive particle to be used.

(Example)

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but in the following, "parts" and "%" are based on mass unless otherwise limited.

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

¹ H-NMR: JEOL RESONANCE ``JNM-ECA600''

Magnetic field strength: 600MHz

Total number of times: 32 times

Solvent: DMSO-d ₆

Sample concentration: 30% by mass

¹³ C-NMR: JEOL RESONANCE ``JNM-ECA600''

Magnetic field strength: 150MHz

Total number of times: 320 times

Solvent: DMSO-d ₆

Sample concentration: 30% by mass

FD-MS: "JMS-T100GC AccuTOF" manufactured by Nihon Denshi Co., Ltd.

Measurement range: m/z=50.00∼2000.00

Rate of change: 25.6mA/min

Final current value: 40mA

Cathode voltage: -10kV

GPC: ``HLC-8320GPC'' manufactured by Tosoh Corporation

Column: Tosoh Corporation "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL"

Detector: RI (differential refractometer)

Measurement conditions: 40℃

Mobile phase: tetrahydrofuran

Flow rate: 1ml/min

Standard: 「PStQuick A」「PStQuick B」「PStQuick E」「PStQuick F」 made by Tosoh Corporation

As a method of calculating the hydroxyl group equivalent and the number of repeating units, calculations from GPC molecular weight measurement and appropriate analysis results of various instruments such as FD-MS and NMR can be exemplified.

Example 1 C12 type (BPA) hydroxy compound Ph-1

In a flask equipped with a thermometer and stirrer, diglycidyl ether of 1,12-dodecanediol (Epoxy equivalent 210g/eq) 210g (0.5 mole) and bisphenol A (hydroxyl equivalent 114g) /eq) 228 g (1.0 mol) was added, the temperature was raised to 140°C over 30 minutes, and then 1 g of a 4% aqueous sodium hydroxide solution was added. Then, the temperature was raised to 150°C over 30 minutes, and further reacted at 150°C for 3 hours. Then, a neutralized amount of sodium phosphate was added to obtain 430 g of a hydroxy compound (Ph-1). This hydroxy compound (Ph-1) has a structure represented by the structural formula (A-1) from the obtained peak of M + = 771 in which m in the general formula (1) corresponds to the theoretical structure of 1 in the mass spectrum. It was confirmed to contain a hydroxy compound. The hydroxyl group equivalent of this hydroxy compound (Ph-1) calculated from GPC was 330 g/eq, and the average value of m in the structural formula (A-1) calculated from the hydroxyl group equivalent was 0.8.

Example 2 C12 type (pyrogallol) hydroxy compound Ph-2

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

Example 3 C12 type (biphenol, tetramethylbiphenol combined use) hydroxy compound Ph-3

228 g (1.0 mol) of bisphenol A in Example 1, 93 g (0.5 mol) of 4,4'-biphenol, and 3,3',5,5'-tetramethylbiphenyl-4,4'-diol Except having changed to 121 g (0.5 mol), it reacted like Example 1, and 415 g of hydroxy compounds Ph-3 were obtained. This hydroxy compound (Ph-3) is represented by the structural formula (A-3) from the obtained peaks of M + = 687, 744, 800 corresponding to the theoretical structure of 1 in the general formula (1) in the mass spectrum. It was confirmed that it contained a hydroxy compound of the structure shown. The hydroxyl group equivalent calculated from GPC of this hydroxy compound (Ph-1) was 318 g/eq, and the average value of m in the structural formula (A-3) calculated from the hydroxyl group equivalent was 0.8.

Example 4 C12 type (tetramethylbiphenol) hydroxy compound Ph-4

As in Example 1 except that 228 g (1.0 mol) of bisphenol A in Example 1 was replaced with 242 g (1.0 mol) of 3,3',5,5'-tetramethylbiphenyl-4,4'-diol. It reacted similarly, and 458g of hydroxy compounds Ph-4 were obtained. This hydroxy compound (Ph-4) is of the structure represented by the above structural formula (A-3) from the obtained peak of M + = 800 corresponding to the theoretical structure of 1 in the general formula (1) m in the mass spectrum. It was confirmed to contain a hydroxy compound. The hydroxyl equivalent of this hydroxy compound (Ph-4) calculated from GPC was 342 g/eq, and the average value of m in the structural formula (A-3) calculated from the hydroxyl equivalent was 0.8.

Example 5 C12 type (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 mol) of bisphenol A in Example 1 was replaced with 160 g (1.0 mol) of 2,7-dihydroxynaphthalene, thereby obtaining 361 g of a hydroxy compound Ph-5. . This hydroxy compound (Ph-5) is of the structure represented by the above structural formula (A-5) from the obtained peak of M+=635 corresponding to the theoretical structure of 1 in the general formula (1) in the mass spectrum. It was confirmed to contain a hydroxy compound. The hydroxyl group equivalent of this hydroxy compound (Ph-5) calculated from GPC was 271 g/eq, and the average value of m in the structural formula (A-5) calculated from the hydroxyl group equivalent was 0.8.

Example 6 C12 type (triphenylolmethane) hydroxy compound Ph-6

The same as in Example 1 except that 228 g (1.0 mol) of bisphenol A in Example 1 was replaced with 292 g (1.0 mol) of triphenylolmethane (“TPM-100”, manufactured by Gunei Chemical Industry Co., Ltd.). By reaction, 498 g of hydroxy compounds Ph-6 were obtained. This hydroxy compound (Ph-6) is of the structure represented by the above structural formula (A-9) from the obtained peak of M + = 900 corresponding to the theoretical structure of 1 in the general formula (1) m in the mass spectrum. It was confirmed to contain a hydroxy compound. The hydroxyl equivalent of this hydroxy compound (Ph-6) calculated from GPC was 192 g/eq, and the average value of m in the structural formula (A-9) calculated from the hydroxyl equivalent was 0.8.

Example 7 C12 type (bis-naphthalenediol) hydroxy compound Ph-7

The reaction was carried out in the same manner as in Example 1 except that 228 g (1.0 mol) of bisphenol A in Example 1 was replaced with 332 g (1.0 mol) of 1,1′-methylenebis-(2,7-naphthalenediol), 522 g of the oxy compound Ph-7 was obtained. This hydroxy compound (Ph-7) has a structure represented by the structural formula (A-10) from the obtained peak of M + = 979 in which m in the general formula (1) corresponds to the theoretical structure of 1 in the mass spectrum. It was confirmed to contain a hydroxy compound. The hydroxyl equivalent of this hydroxy compound (Ph-7) calculated from GPC was 139 g/eq, and the average value of m in the structural formula (A-10) calculated from the hydroxyl equivalent was 0.8.

Comparative Example 1 Hydroxy compound Ph-8 of C6 type (BPA)

210 g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol in Example 1 was added to diglycidyl ether of 1,6-hexanediol (manufactured by DIC Corporation: brand name EPICLON 726D, epoxy equivalent) 124 g/eq) Except having changed it to 124 g (0.5 mol), it reacted like Example 1, and 340 g of hydroxy compounds Ph-8 were obtained. As for this hydroxy compound Ph-8, a peak of M+=687 was confirmed in the mass spectrum. The hydroxyl group equivalent calculated from GPC of this hydroxy compound Ph-8 was 262 g/eq.

Comparative Example 2 Hydroxy compound Ph-9 of type C9 (BPA)

210 g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol in Example 1 was added to diglycidyl ether of 1,9-nonanediol (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.: epoxy equivalent 156 g/eq) Except having changed to 156 g (0.5 mol), it reacted similarly to Example 1, and obtained 350 g of hydroxy compounds Ph-9. As for this hydroxy compound Ph-9, a peak of M+=729 was confirmed in the mass spectrum. The hydroxyl group equivalent calculated from GPC of this hydroxy compound Ph-9 was 328 g/eq.

Formulation Example 1 Preparation of adhesive composition

100 parts of Epicron 850S (manufactured by DIC Corporation, bisphenol A type epoxy resin) as an epoxy resin, 5.59 parts of DICY (manufactured by Mitsubishi Chemical, ``DICY7'') as a curing agent, and DCMU (DIC Corporation) as a curing accelerator. 0.85 parts of B-605-IM, manufactured by Shiki Corporation, were uniformly mixed with a mixer ("Awatori Rentaro ARV-200" manufactured by Shinki Corporation) 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. The cold rolled steel sheet ("SPCC-SB" manufactured by TP Kiken Co., Ltd.) was immersed at room temperature for 60 minutes without degreasing, and then dried at room temperature for 5 hours.

<Tensile shear test>

The adhesive layer obtained in Formulation Example 1 was applied to one of two cold-rolled steel sheets subjected to primer treatment ("SPCC-SB" manufactured by TP Kiken Co., Ltd., 1.0 mm×25 mm×100 mm), and a spacer As a result, glass beads ("J-80" manufactured by Porters Balotini Corporation) were added, and another aluminum plate was bonded (adhesive area: 25 mm x 12.5 mm). This was heated and cured at 170° C. for 30 minutes to obtain a test piece. Adhesiveness was evaluated by performing a tensile shear test using the test piece. The test was performed according to JIS K 6850, and the maximum point stress and the maximum point strain were compared.

In addition, as Comparative Example 5, a laminate was prepared only with the adhesive composition without using a primer.

<T-type peeling test>

The adhesive layer obtained in Formulation Example 1 was applied to one of two cold-rolled steel sheets subjected to primer treatment ("SPCC-SB" manufactured by TP Kiken Co., Ltd., 0.5 mm×25 mm×200 mm), and a spacer As a result, a glass bead ("J-80" manufactured by Porters Balotini Corporation) was added, and another aluminum plate was bonded (adhesive area: 25 mm x 150 mm). This was heated and cured at 170° C. for 30 minutes to obtain a test piece. Adhesiveness was evaluated by performing a T-type peeling test using the test piece. The test was performed according to JIS K 6854-3, and the average stress was compared.

In addition, as Comparative Example 5, a laminate was prepared only with the adhesive composition without using a primer.

[Table 1]

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

The hydroxy compound A of the present invention can exhibit high adhesion and primer properties even on a metal surface, particularly a contaminated metal surface.

Claims (14)

Hydroxy compound A having the structure of general formula (1).

···(One)
(In formula (1), Ar each independently represents a structure having an unsubstituted or substituted aromatic ring,
R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
R ₃ and R ₄ each independently represent a hydroxyl group or a methyl group,
n is an integer of 11 to 16, and m is an average value of the number of repetitions, and is 0.5 to 10.
(However, it does not matter if each repeating unit present in the repeating unit is the same or different)) The method of claim 1,
In formula (1), Ar is any one structure represented by the following formula (2), hydroxy compound A.

···(2)
(In formula (2), the aromatic ring may be substituted or unsubstituted, and * represents a bonding point) The method according to claim 1 or 2,
In formula (1), the hydroxy compound A in which Ar further has a hydroxyl group. A composition comprising the hydroxy compound A according to any one of claims 1 to 3. The method of claim 4,
In addition, a composition containing a compound that reacts with the hydroxy compound A. The method of claim 5,
The composition, wherein the compound reacting with the hydroxy compound A is an epoxy compound and/or an isocyanate compound. The method according to any one of claims 4 to 6,
In addition, a composition containing a filler. A cured product obtained by curing the composition according to any one of claims 4 to 7. A laminate comprising a substrate and a layer of the composition according to any one of claims 4 to 7. The method of claim 9,
The laminate, wherein the substrate is a metal or metal oxide. The method according to claim 8 or 9,
The substrate, the composition layer according to any one of claims 4 to 7, and the second substrate is a laminate formed by laminating in this order, the substrate is a metal or metal oxide, and the second substrate is a plastic layer, Laminate. The method according to any one of claims 8 to 10,
The substrate, the composition layer according to any one of claims 4 to 7, and the adhesive layer and the second substrate are laminated in this order, and the substrate is a metal or metal oxide, and the second substrate is A plastic layer, a laminate. An electronic member comprising the laminate according to any one of claims 8 to 10. A primer for metal or metal oxide, comprising the hydroxy compound A according to any one of claims 1 to 3.