Compounds, curable compositions, and adhesion improvers

Abstract

The present invention provides compounds, curable compositions, and adhesion enhancers that can improve adhesion to metals. [Solution] A compound (A) represented by the following formula (I), a curable composition, and an adhesion improver. JPEG2026064080000011.jpg3373 (in formula (I), R 1 ~R 5 Each of these independently represents a hydrogen atom or a hydroxyl group, however, R 1 ~R 5 At least two of the adjacent ones represent a hydroxyl group, L 1 (where n is an alkylene with 1 to 20 carbon atoms, and n is an integer of 1 or 2.)

Description

[Technical Field]

[0001] This invention relates to compounds, curable compositions, and adhesion improvers. [Background technology]

[0002] In recent years, with the increasing integration and miniaturization of semiconductor devices, the surface protective layer and interlayer insulating layer of semiconductor devices are required to have heat resistance, mechanical properties, and adhesion to metal wiring (Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2024-4027 [Overview of the project] [Problems that the invention aims to solve]

[0004] There is still room for further development of materials that satisfy the requirements for adhesion to metals, and new compounds are needed.

[0005] Therefore, the present invention aims to provide compounds, curable compositions, and adhesion improvers that can improve adhesion to metals. [Means for solving the problem]

[0006] The inventors have discovered a novel compound (A) having a specific structure in which at least two adjacent hydroxyl groups and an epoxy or oxetanyl group, and have further discovered that this compound has properties that improve adhesion to metals, thereby completing the present invention.

[0007] The present invention [1] Compound (A) represented by the following formula (I), [ka] (In formula (I), R , , ,

[0011] , , ~R 5 each independently represents a hydrogen atom or a hydroxyl group, provided that R 1 ~R 5 at least two adjacent ones of which represent hydroxyl groups, and L 1 is an alkylene having 1 to 20 carbon atoms, and n is an integer of 1 or 2.) [2] A curable composition containing the compound (A) described in [1] above, [3] The curable composition described in [2] above, further containing an epoxy resin (B) and a curing agent (C), [4] An adhesion improver for metal containing the compound (A) described in [1] above, and [5] The adhesion improver described in [4] above, wherein the metal is copper or stainless steel relates to.

Effect of the Invention

[0008] According to the present invention, it is possible to provide a compound, a curable composition, and an adhesion improver for metal that can improve the adhesion to metal.

Modes for Carrying Out the Invention

[0009] In this specification, the adhesiveness (the magnitude of the adhesive force) means, for example, in two base materials joined by an adhesive, the interfacial peeling (adhesion) between the adhesive and the base material and the force (toughness) required when the resin as the adhesive is broken. combined force. Generally, when measuring adhesiveness, the joining of the two base materials collapses by breaking the adhesive or cutting the bond between the base material and the adhesive. Adhesiveness is an index of the strength of the joining of two base materials.

[0010] In this specification, when a numerical range is indicated using "~", it includes the numerical values at both ends.

[0011] [Compound (A)] In one aspect of the present invention, a compound (A) represented by the following formula (I) (hereinafter, also simply referred to as compound (A)) is provided. [Chemical Formula] (In formula (I), R 1 ~R 5 each independently represents a hydrogen atom or a hydroxyl group, provided that at least two adjacent ones of R 1 ~R 5 represent a hydroxyl group, L 1 is an alkylene having 1 to 20 carbon atoms, and n is an integer of 1 or 2.)

[0012] "Alkylene having 1 to 20 carbon atoms" means a linear or branched divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and may be "alkylene having 1 to 8 carbon atoms", "alkylene having 1 to 6 carbon atoms", "alkylene having 1 to 4 carbon atoms", "alkylene having 1 to 3 carbon atoms", or "alkylene having 1 to 2 carbon atoms". Specific examples of "alkylene having 1 to 20 carbon atoms" include, for example, methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, 1-methylmethylene, 1-ethylmethylene, 1-propylmethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, etc.

[0013] In one embodiment, in formula (I), R 1 ~R 5 is preferably such that two adjacent ones of R 1 ~R 5 represent a hydroxyl group and the remaining three are hydrogen atoms. Among them, it is more preferable that compound (A) in which R 3 and R 2 or R 4 is a hydroxyl group and the rest are hydrogen atoms.

[0014] ] In one embodiment, in formula (I), L 1 is preferably a linear alkylene having 1 to 4 carbon atoms, and more preferably a linear alkylene having 1 to 2 carbon atoms.

[0015] In one embodiment, in formula (I), n is preferably 1.

[0016] Compound (A) can be used as an adhesion improver together with resins, paints, resists, coatings, etc., as described later, and is particularly suitable as an adhesion improver when incorporated into curable compositions based on curable resins. The amount of compound (A) added is not particularly limited and can be appropriately determined depending on the material (resin, paint, resist, coating, etc.) and the intended use.

[0017] The mechanism by which compound (A) functions as an adhesion enhancer to metals is not clear, but it can be inferred that adjacent hydroxyl groups in the aromatic ring are oriented on the metal surface, acting as anchors and exhibiting strong adhesion. Furthermore, if an oxide of the metal is present on the metal surface, it can be inferred that strong adhesion is achieved through hydrogen bonding between the metal oxide and the phenolic hydroxyl groups.

[0018] The type of metal in which compound (A) functions as an adhesion enhancer is not particularly limited, but examples include copper, iron, stainless steel (SUS), aluminum, titanium, and their alloys. Among these, compound (A) has a high adhesion-enhancing effect on copper surfaces, and it is preferable to use compound (A) as an adhesion enhancer on copper surfaces.

[0019] Compound (A) is a newly synthesized compound in the present invention and can be synthesized by a known esterification reaction between the corresponding hydroxybenzoic acid and the corresponding alkyl halide having a cyclic ether.

[0020] Furthermore, as will be described later as a reference example, in addition to compound (A), compound (A'), represented by the following formula (I'), was also discovered as a novel compound obtained by synthesizing it in the same manner as compound (A) as another embodiment of the present invention. [ka] (In formula (I'), R' 1 ~R' 5 Each of these independently represents a hydrogen atom or a hydroxyl group, and L'1 R' is an alkylene with 1 to 20 carbon atoms, where n is an integer of 1 or 2; however, R' 1 ~R' 5 Not all of them are hydrogen atoms, and this excludes those that fall under compound (A).

[0021] [Curable composition] In one embodiment of the present invention, a curable composition containing the compound (A) described above is provided. This curable composition contains a curable component and a curing agent (C), and the curable component may be compound (A) alone, or it may contain other curable components such as a curable resin. This curable composition may also contain other components such as a curing accelerator, filler, coupling agent, thixotropic agent, diluent, and solvent. The other curable component and other components are not particularly limited, and those well known in the art can be appropriately selected depending on the desired application of the cured film. Furthermore, the other curable component and other components may be used individually, or two or more may be used in combination.

[0022] <Curing component> (Compound (A)) The compound (A) represented by formula (I) used in the curable composition is as described above in the section [Compound (A)]. Compound (A) may be used individually or in combination of two or more types.

[0023] The lower limit of the content of compound (A) in the curable composition is not particularly limited, but from the viewpoint of improving adhesive strength, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, out of 100 parts by mass of the total of the curable resin and compound (A) described later. Furthermore, the upper limit of the content of compound (A) in the curable composition is not particularly limited, but in order to ensure a sufficient pot life, it is preferably 10 parts by mass or less, and more preferably 8 parts by mass or less, out of 100 parts by mass of the total of the curable resin and compound (A) described later.

[0024] (curable resin) Examples of curable resins used in curable compositions include epoxy resins, acrylic resins, styrene resins, amide resins, amide epoxy resins, alkyd resins, and phenolic resins. Those well-known in this art can be appropriately selected depending on the desired application of the cured film. Among these, epoxy resin (B) is preferred due to its compatibility with compound (A). The curable resins may be used individually or in combination of two or more.

[0025] The epoxy resin (B) is not particularly limited and includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, aliphatic type epoxy resin, glycidylamine type epoxy resin, etc. Each epoxy resin (B) may be used individually or in combination of two or more types.

[0026] The lower limit of the content of the curable resin in the curable composition is not particularly limited, but from the viewpoint of ensuring a sufficient pot life, it is preferably 90 parts by mass or more, more preferably 92 parts by mass or more, and even more preferably 95 parts by mass or more, out of 100 parts by mass of the total of compound (A) and the curable resin. Furthermore, the upper limit of the content of the curable resin in the curable composition is not particularly limited, but from the viewpoint of improving adhesive strength, it is preferably 99 parts by mass or less, more preferably 97 parts by mass or less, and even more preferably 96 parts by mass or less, out of 100 parts by mass of the total of compound (A) and the curable resin.

[0027] <Hardening agent (C)> When used in a curable composition, the curing agent (C) is not particularly limited, but examples include thermosetting agents commonly used in this art, such as polyamines, polycarboxylic acids, and polyhydric alcohols. Each curing agent (C) may be used alone, or two or more may be used in combination. Among these, polyamines are preferred from the viewpoint of excellent transparency, gloss, and adhesion of the resulting cured product.

[0028] As the polyamine-based curing agent, either aliphatic amines or aromatic amines can be used, but aliphatic amines are preferred, and aliphatic compounds having two or more amine groups are more preferred. Aliphatic polyamines may have an alicyclic structure.

[0029] Suitable aliphatic polyamines include, but are not limited to, isophoronediamine, norbornenediamine, 1,3-bisaminomethylcyclohexane, diethylenetriamine, triethylenetetramine, 4,4'-diaminocyclohexylmethane, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, tetraethylenepentamine, pentaethylenehexamine, polyoxyalkylenediamine such as polyoxyethylenediamine and polyoxypropylenediamine, polyoxyalkylenediamine such as polyoxyethylenetriamine and polyoxypropylenetriamine, and aminoethylated acrylic polymers. These curing agents may be used individually or in combination of two or more types. Among these aliphatic polyamines, isophorone diamine, polyoxyalkylenediamine, 1,3-bisaminomethylcyclohexane, diethylenetriamine, triethylenetetramine, and 4,4'-diaminocyclohexylmethane are more preferred from the viewpoint of excellent transparency, gloss, and adhesion of the resulting cured product, and isophorone diamine, 1,3-bishuminomethylcyclohexane, diethylenetriamine, and triethylenetetramine are even more preferred.

[0030] When using a curing agent (C), the lower limit of its content in the curable composition is not particularly limited, but from the viewpoint of sufficiently curing the curable composition and preventing the presence of unreacted curable resin in the cured product, it is preferably 4 parts by mass or more, and more preferably 6 parts by mass or more, per 100 parts by mass of the total of compound (A) and curable resin. Similarly, the upper limit of the content of curing agent (C) in the curable composition is not particularly limited, but from the viewpoint of sufficiently curing the curable composition and preventing the presence of unreacted curing agent (C) in the cured product, it is preferably 12 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the total of compound (A) and curable resin.

[0031] <Other ingredients> (Curing accelerator) Specific examples of curing accelerators include imidazole compounds, amine compounds, and triphenylphosphine. These curing accelerators may be used individually or in combination of two or more.

[0032] (Filler) Specific examples of fillers include silica, alumina, calcium carbonate, kaolin clay, talc, aluminum hydroxide, and iron powder. These fillers may be used individually or in combination of two or more.

[0033] (Coupling agent) Specific examples of coupling agents include silane coupling agents and titanate coupling agents. These coupling agents may be used individually or in combination of two or more.

[0034] (Stimulant) Specific examples of thixotropic agents include fumed silica and anti-dripping agents. These thixotropic agents may be used individually or in combination of two or more.

[0035] (Additives) Specific examples of additives include coloring pigments, defoamers, leveling agents, tackifiers, rubber particles, liquid rubber, elastomers, and flame retardants. These additives may be used individually or in combination of two or more.

[0036] (Diluent) Specific examples of diluents include reactive diluents (monoeposides) and non-reactive diluents (plasticizers). These diluents may be used individually or in combination of two or more.

[0037] (solvent) When used in curable compositions, the solvent is not particularly limited, but from the viewpoint of maintaining good adhesive strength, a solvent with a boiling point of 100°C or higher, more preferably 110°C or higher, even more preferably 150°C or higher, and particularly preferably 200°C or higher is preferred. Furthermore, from the viewpoint of maintaining good adhesive strength, a ketone-based solvent having a ketone group (C=0 structure) is also preferred. Specific examples of such solvents include diethylene glycol monobutyl ether (boiling point: 230°C), methyl isobutyl ketone (boiling point: 116°C), diisobutyl ketone (boiling point: 168°C), cyclohexanone (boiling point: 156°C), and diacetone alcohol (boiling point: 169°C). These solvents may be used individually or in combination of two or more. [Examples]

[0038] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Furthermore, the compound names shown in the following examples and comparative examples do not necessarily follow IUPAC nomenclature. In the examples and comparative examples, ppm indicates weight percentage.

[0039] Example 1: Synthesis of Compound A1 [ka] 25.00 g (0.181 mol) of 3,4-dihydroxybenzoic acid (DHBA), 16.75 g (0.181 mol) of epichlorohydrin, 37.50 g of dimethyl sulfoxide (DMSO), and 15.21 g (0.181 mol) of NaH3CO3 were added to a flask. After reacting at 60°C for 14 hours, 125 g of ethyl acetate was added, followed by three washes with water. The solvent was then removed by distillation to obtain the target compound A1 as a yellow solid. The yield was 63%. 1 The H-NMR data is shown below. 1 H-NMR (CDCl3, ppm): 3.69 (2H, ddd), 4.02 (1H, quin), 4.21 (2H, d), 6.82 (1H, d), 7.37 (1H, dd), 7.44 (1H, d), 9.36 (1H, br), 9.80 (1H, br).

[0040] Reference Example 1: Synthesis of Compound A'1 [ka] Compound A'1 was obtained as a brown liquid in the same manner as compound A1 in Example 1, except that 3,4-dihydroxybenzoic acid was replaced with 3,5-dihydroxybenzoic acid. The yield was 39%. 1 The H-NMR data is shown below. 1 H-NMR(CDCl3, ppm): 3.68 (2H, ddd), 4.01-4.05 (1H, m), 4.23 (2H, dd), 6.45 (1H, t), 6.86 (2H, d), 9.63 (2H, S).

[0041] Reference Example 2: Synthesis of Compound A'2 [ka] Compound A'2 was obtained as a white solid in the same manner as compound A1 in Example 1, except that 3,4-dihydroxybenzoic acid was replaced with 4-hydroxybenzoic acid. The yield was 65%.1 The H-NMR data is shown below. 1 H-NMR (CDCl3, ppm): 3.70 (2H, ddd), 4.01-4.05 (1H, m), 4.22 (2H, d), 6.86 (2H, d), 7.86 (2H, d), 10.34 (1H, s).

[0042] Comparative Example 1: Synthesis of Compound A''1 [ka] The target compound A''1 was obtained as a yellow liquid in the same manner as compound A1 in Example 1, except that 3,4-dihydroxybenzoic acid was replaced with benzoic acid. The yield was 57%. 1 The H-NMR data is shown below. 1 H-NMR (CDCl3, ppm): 3.69 (2H, ddd), 4.21 (1H, quin), 4.45 (2H, d), 7.42 (2H, t), 7.56 (1H, t), 8.03 (2H, dd).

[0043] Comparative Example 2: Synthesis of Compound A''2 [ka] 3.0 g (0.016 mol) of 3-hydroxytyramine hydrochloride, 1.60 g (0.016 mol) of triethylamine, and 8.40 g of dimethylformamide were stirred at room temperature. The precipitated salt was filtered off, and 5.39 g of epoxy resin (bisphenol A type epoxy resin (trade name: JER-828EL, manufactured by Mitsubishi Chemical Corporation)) was added to the filtrate. The mixture was reacted at room temperature for 12 hours. The solvent was then removed by distillation to obtain the target compound A''2 as a yellow liquid. The yield was 95%.

[0044] Examples 2-1 and 2-2, Reference Examples 2-1 and 2-2, Comparative Examples 2-1 to 2-4: Preparation of curable compositions Mixtures were prepared by mixing compound (A), compound (A'), or compound (A") and epoxy resin (B) (JER-828EL) according to the compositions shown in Table 1. To each mixture, curing agent (C) (dieethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd.)) was added as a curing catalyst and mixed further to obtain each curable composition.

[0045] <Adhesion Test> <<Preparation of test specimens>> Mixtures were prepared by mixing compound (A) or compound (A') and epoxy resin (B) according to the compositions listed in Table 1. A curing agent (C) was added to each mixture as a curing catalyst and further mixed. Then, two copper test plates (copper-clad laminated substrate (cut substrate), glass epoxy single-sided / 100×100×1.6t, No.31, manufactured by Sunhayato Co., Ltd., cut to 2.5cm×10cm) were prepared as substrates. The mixture was injected into an 8mm diameter circular hole made of silicone in one of the plates, and the other test plate was placed on top so as to be in contact with the mixture. The combined test plates were then exposed to a dryer at 100°C for 30 minutes to cure each mixture, and these were used as test specimens. In addition, test specimens were prepared in the same manner using a commercially available SUS substrate (stainless steel surface finish plate BA (mirror finish), manufactured by TP Giken Co., Ltd.) as the substrate.

[0046] ≪Test Method≫ In accordance with JIS K 6850:1999 "Adhesives - Test method for tensile shear bond strength of rigid adherends," one test plate constituting the test specimen was pulled in its longitudinal direction, while the other test plate was pulled in the opposite direction to the direction in which the first test plate was pulled, and the bond strength between the materials was measured. The pulling speed was set to 5.0 mm / second for all test specimens. The bond strength of each test specimen was measured either immediately after preparation or after being left to stand in water for 24 hours.

[0047] ≪Results≫ The results are shown in Table 1. From the results of Examples 2-1 to 2-3, Reference Examples 2-1 to 2-2, and Comparative Examples 2-1 to 2-4, it can be seen that compound (A) according to the present invention has the effect of improving the adhesion of the cured product to metals, particularly copper. Furthermore, from the test results of the adhesion strength after standing in water on SUS substrates in Examples 2-1 to 2-3 and Comparative Example 2-2, it can be seen that compound (A) according to the present invention also has the effect of improving the adhesion of the cured product to SUS. Moreover, from the test results of the adhesion strength after standing in water on SUS substrates in Examples 2-1 to 2-3 and Comparative Example 2-2, it can be seen that compound (A) according to the present invention can maintain its adhesive strength even in the harsh environment of water compared to the comparative examples. Note that the adhesion test could not be performed for Comparative Example 2-4 because the composition did not harden.

[0048] [Table 1]

Claims

1. Compound (A) represented by the following formula (I). 【Chemistry 1】 (In formula (I), R 1 ~R 5 Each of these independently represents a hydrogen atom or a hydroxyl group, except R 1 ~R 5 At least two of the adjacent ones represent a hydroxyl group, L 1 (where n is an alkylene with 1 to 20 carbon atoms, and n is an integer of 1 or 2.)

2. A curable composition comprising compound (A) as described in claim 1.

3. The curable composition according to claim 2, further comprising an epoxy resin (B) and a curing agent (C).

4. An adhesion enhancer for metals, comprising compound (A) as described in claim 1.

5. The adhesion improver according to claim 4, wherein the metal is copper or stainless steel.

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