JP2021054921A - Epoxy resin composition - Google Patents

Abstract

To provide an epoxy resin composition which cures within a certain time and exhibits high adhesive strength and stable adhesiveness to hard vinyl chloride.SOLUTION: There is provided an epoxy resin composition for adhering a hard vinyl chloride tube including: 5 to 90 wt.% of a bisphenol-based epoxy compound as a main agent; 0.1 to 50 wt.% of a thiol compound as a curing agent; 0.1 to 50 wt.% of a tertiary amine; and 0.1 to 50 wt.% of an amino group-terminated nitrile-butadiene rubber (: ATBN), wherein the amount of ATBN is smaller than that of the bisphenol epoxy compound.SELECTED DRAWING: None

Description

The present invention relates to an epoxy resin composition suitable for joining hard vinyl chloride pipes (PVC pipes) for water and sewage systems.

Patent Document 1 is a piping jig publication that can perform piping work for a plurality of types of pipes having different diameters with one type and does not easily come off after winding. Since the pipe material is hard vinyl chloride and it is difficult to bond hard vinyl chloride, joining is performed using a jig. The jig is fixed by tightening the wire rope, but the tightening force varies from person to person unless a torque wrench is used, and the joining accuracy remains uncertain.
Therefore, in order to reduce the number of jigs for joining and to eliminate the variation in mounting accuracy due to individual differences in tightening, there has been a demand for an adhesive method that can be joined only with an adhesive.

On the other hand, although it is an epoxy resin composition, various types of epoxy compositions are marketed as epoxy adhesives, but as mentioned above, hard vinyl chloride is difficult to adhere and cures within a certain period of time to hard chloride. There was no epoxy resin composition showing high adhesive strength and stable adhesiveness to vinyl.

Patent Document 2 is a publication of an epoxy resin composition for bonding a voice coil / bobbin of a speaker. The curing time was long and the adhesiveness to hard vinyl chloride was not confirmed.
Patent Document 3 describes that epoxy resins are used as paints for automobiles, paints for ships, anticorrosion paints, adhesives for aircraft, adhesives for electrical and electronic parts, adhesives for civil engineering and construction, and adhesives for wood processing. There is. In Patent Document 4, the epoxy resin composition is useful as, for example, a sealing agent for electric parts or electronic parts, a coating agent, a casting agent, a dipping agent and an adhesive, a caulking agent for civil engineering and construction, a paint, a lining agent, and the like. There is a description that there is.
Although all the documents have improved the curing time, the adhesiveness to hard vinyl chloride has not been confirmed, and there is room for improvement in the adhesiveness to hard vinyl chloride.

JP-A-5-126281 JP-A-53-149315 Japanese Patent Application Laid-Open No. 60-181123 Japanese Patent Application Laid-Open No. 63-186726 JP 2018-511670 Japanese Patent Application Laid-Open No. 4-275383 JP 2015-127356 JP-A-9-111220

Patent Document 5 describes a two-component structural epoxy adhesive which exhibits high-speed room temperature curing and is cured to form a bond having excellent high-temperature characteristics. In the specification, a thiol compound is mentioned as an arbitrary suitable epoxy curing agent, but there is no example of implementation and there is room for improvement in terms of curing time.

Patent Document 6 cites a thioether compound of 4,4'-thiodianiline instead of a thiol compound as a suitable aromatic amine curing agent. There was no example of using this compound as a curing agent, and there was room for improvement in terms of curing time.

Patent Document 7 is excellent in workability because it can be cured by light irradiation, storage stability is good, and the time (usable time) until a sufficient adhesive force can be obtained can be adjusted. , A publication relating to an adhesive sheet. On the other hand, joining of PVC pipes and the like for water and sewage may be performed at a factory or at an outdoor construction site. The adhesive sheet of Patent Document 7 requires a light irradiator, and bringing a large-scale light irradiator outdoors is unsuitable because of a physical load.
Further, an example in which biguanidine, which is a secondary amine, is generated by light irradiation is shown, but an example in which a tertiary amine is added is not shown.
Further, Patent Document 7 describes in the specification that a polyvinyl chloride-based resin can be used as a base material, but does not show an example in which hard vinyl chlorides are bonded to each other.

Patent Document 8 is a publication that provides an underfloor repair method having a small number of steps and construction time, and good adhesiveness and hot water adhesion for a long period of time, and an adhesive used for the underfloor repair of a bathtub.
Although it is described as an adhesive having excellent adhesiveness and capable of shortening the curing time, curing within 60 minutes was impossible. In addition, since a large amount of amino group-terminated nitrile-butadiene rubber (: ATBN) having a large active hydrogen equivalent is added, the cured product is very flexible, and the hardness is finally adjusted with cement. Although it is suitable for bonding soft vinyl chloride sheets, it is not suitable for bonding hard vinyl chloride tubes, which require high adhesive strength and stable adhesiveness.

It is an object of the present invention to provide an epoxy resin composition which is cured within a certain period of time and the cured product exhibits high adhesive strength and stable adhesiveness to hard vinyl chloride.

The present inventor is an epoxy resin composition for adhering a hard vinyl chloride tube, in which the main agent is 5 to 90% by weight of a bisphenol epoxy resin and 0.1 to 50% by weight of a thiol compound as a curing agent. It contains 0.1 to 50% by weight of tertiary amine, 0.1 to 50% by weight of amino group-terminated nitrile-butadiene rubber (: ATBN), and ATBN is less than that of the bisphenol epoxy resin. An epoxy resin composition for adhering a hard vinyl chloride tube, which is an amount, was obtained.

The epoxy resin composition of the present invention is cured within a certain period of time, and the cured product exhibits high adhesive strength and stable adhesiveness to hard vinyl chloride, and is therefore most suitable for joining hard vinyl chloride.

The main agent is a bisphenol-based epoxy compound, the curing agent is a thiol compound, a tertiary amine, and an amino group-terminated nitrile-butadiene rubber (: ATBN), which is an epoxy resin composition for bonding PVC pipes.

The epoxy resin composition of the present application is a two-component type.
The main agent contains a bisphenol epoxy compound. Examples of the bisphenol-based epoxy resin include bisphenol A diglycidylate, bisphenol F diglycidylate, bisphenol E diglycidylate, and bisphenol S diglycidylate, and may be hydrogenated (hydrogenated) type.

．．．（１） The basic structural formula of the bisphenol A type epoxy compound is shown in the formula (1). Bisphenol A type epoxy compounds have various grades depending on the degree of polymerization.
These may be used alone or in combination of two or more.
Specifically, from Mitsubishi Chemical Co., Ltd., product name: 825, product name: 827, product name: 828 (epoxy equivalent: 190), product name: 834, product name: 1001 (epoxy equivalent: 475), The amount of the bisphenol epoxy compound contained in the main agent on the market, such as product name: 1002 and product name: 1010, is 5 to 90% by weight, more preferably 10 to 80% by weight of the whole.

.. .. .. (1)

A diluent can also be added to the main agent. Examples of the diluent include glycidylated aliphatic compounds and glycidylated ether compounds, and the glycidylated number is arbitrary. As a typical example, manufactured by Yokkaichi Synthetic Co., Ltd., trade name: DY-BP (butyl glycidyl ether), trade name: CY-BP (butyl glycidyl ether), trade name: Epogosei EN (C12-13 mixed alcohol glycidyl ether), product Name: Epogosei AN (C12-13 mixed alcohol glycidyl ether), trade name: Epogosei 2EH (2-ethylhexyl glycidyl ether), trade name: Epogosei HD (M) (1,6-hexanediol diglycidyl ether) and the like. ..
The diluent has the meaning of adjusting the viscosity and adjusting the hardness, and the amount added is arbitrary.

The curing agent contains a thiol compound, a tertiary amine, and an amino group-terminated nitrile-butadiene rubber (: ATBN). As the thiol compound, manufactured by Mitsubishi Chemical Corporation, trade name: QX-11, trade name: QX-40 (active hydrogen equivalent: 130), Cognis Iberia S. et al. A. U.S. Manufactured by the company, trade name: KYE-C380, trade name: KYE-C380LO (active hydrogen equivalent: 280) and the like can be mentioned.
The amount added is 0.1 to 50% by weight of the whole, more preferably 1 to 40% by weight of the whole.

Examples of commercially available products of the tertiary amine include Evonik Japan Co., Ltd., trade name: Ankamin 1110, trade name: Ankamin K-54, and trade name: Ankamin K-61B.
The amount added is 0.1 to 50% by weight of the whole, more preferably 1 to 40% by weight of the whole.

Examples of the ATBN include CVC Thermoset Specialties, trade name: HyperATBN 1300 × 16 (active hydrogen equivalent: 850), trade name: HyperATBN 1300 × 35, and the like. Further, examples of the amine containing ATBN include those manufactured by Evonik Japan, Inc., trade name: Sanmide 336 (active hydrogen equivalent: 90) and the like. Sanmide 336 is a mixture of 65-70% polyamideamine, 10-15% ATBN, and 5-15% tetraethylenepentamine.
In the case of Sanmide 336, the amount added is 0.1 to 50% by weight, more preferably 1 to 40% by weight of the whole. Due to the adhesive strength, ATBN must be in a smaller amount than the bisphenol epoxy resin.

As the curing agent, an amine compound other than the thiol compound, the tertiary amine, and the amino group-terminated nitrile-butadiene rubber (: ATBN) can be used in combination.
Specific product names of amine-based curing agents are manufactured by Ebonic Japan, product name: Ancamide 260A (active hydrogen equivalent: 120), product name: Ancamide 350A, product name: Ancamide 375A, product name: Ancamide 910. , Product name: Ancamide 2050, Product name: Ancamide 2137, Product name: Ancamide 2353, Product name: Ancamide 2396, Product name: Ancamide 2426, Product name: Ancamide 2445, Product name: Ancamide 910, Product name: Ancamine 1110, Product Name: Ankamin 1561, Product name: Ankamin 1618, Product name: Ankamin 1618F, Product name: Ankamin 1693, Product name: Ankamin 1704, Product name: Ankamin 1769, Product name: Ankamin 1884, Product name: Ankamin 1895, Product name: Ankamin 1934, Product name: Ankamin 2071, Product name: Ankamin 2072, Product name: Ankamin 2074, Product name: Ankamin 2075, Product name: Ankamin 2143, Product name: Ankamin 2280, Product name: Ankamin 2199, Product name: Ankamin 2205 , Product name: Ankamin 2228, Product name: Ankamin 2368, Product name: Ankamin 2405, Product name: Ankamin 2432, Product name: Ankamin 2422, Product name: Ankamin 2502, Product name: Ankamin 2505, Product name: Ankamin 2609, Product name Name: Ankamin 1618, Product name: Ankamin 1884, Product name: Ankamin 1934, Product name: Ankamin 2074, Product name: Ankamin 2143, Product name: Ankamin 2280, Product name: Ankamin 2596, Product name: Ankamin 2643, Product name: Ankamin 2644, Product name: Ankamin 2706, Product name: Ankamin 2730, Product name: Ankamin 2049, Product name: Ankamin 2264, manufactured by PIT Japan, Product name: Hardener PH-770, Product name: Hardner PH -776P, Product Name: Hardener PH777P, Product Name: Hardener PH-780, Product Name: Hardener PH-781, Product Name: Hardener PH782, Product Name: Hardener PH785, Product Name: Hardener PH-798, Product Name: Hardener KA -861, trade name: Hardener KA-935 and the like.

A solvent can be added to the main agent and the curing agent. Solvents that can be added include methyl acetate, ethyl acetate, butyl acetate, benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-hexane, methanol, ethanol, isopropyl alcohol, n-butanol, benzyl alcohol, and propylene glycol. Solvents such as monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, and propylene carbonate can be mentioned. These two or more kinds of solvents can also be used in combination. The diluting solvent has the meaning of adjusting the viscosity, and the amount added is arbitrary.

The epoxy resin composition includes calcium carbonate, talc, silica, kaolin, calcined kaolin, clay, calcium silicate, calcium sulfate, aluminum oxide (alumina), aluminum hydroxide, aluminum silicate, titanium oxide, zinc oxide, magnesium carbonate, magnesium silicate, Inorganic fillers such as zeolite, glass beads, and silas balloon can be added.
In addition, polyethylene, polypropylene, polymethyl methacrylate, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-vinyl acetate copolymer, nylon, polyethylene terephthalate, polybutylene terephthalate. , Polystyrene, ABS resin, acrylic nitrile-styrene copolymer, polypropylene and other organic fillers can also be added.
The amount of the filler added is 50 to 90% by weight, more preferably 55 to 85% by weight of the whole.

In the epoxy resin composition of the present application, water can be added when the two liquids are mixed in order to promote curing. The amount added is 0.1 to 10%, more preferably 1 to 5% of the total amount.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but specific examples are shown and the present invention is not particularly limited thereto. The number of copies is all by weight.

Preparation of main agent of Example 1 11.0 parts by weight of 828 of bisphenol A type epoxy compound, 3.4 parts by weight of 1001 of bisphenol A type epoxy resin, 1.7 parts by weight of benzyl alcohol, calcium carbonate manufactured by Shiraishi Calcium Co., Ltd. Product name: BF200 by 27.2 parts by weight, talc manufactured by Nippon Tarku Co., Ltd. Product name: Simgon by 6.7 parts by weight, these were weighed in a stirring container and stirred until uniform to obtain the main agent of Example 1. .. A planetary mixer was used for stirring.

Preparation of base agents of Examples 2 to 6 and Comparative Examples 1 to 5 The main agents of Examples 2 to 6 and Comparative Examples 1 to 5 were prepared in the same procedure as in the preparation of the main agent of Example 1 at the blending ratios shown in Tables 1 and 2. Was produced.

Preparation of Hardener of Example 1 3.3 parts by weight of Sanmide 336, 3.8 parts by weight of Ancamide 260A, 4.5 parts by weight of KYE-C380LO, 1.7 parts by weight of Ancamin K54, 0.5 parts by weight of benzyl alcohol. 25.7 parts by weight of BF200 and 10.5 parts by weight of Simgon were weighed in a stirring container and stirred until uniform to obtain a curing agent of Example 1. A planetary mixer was used for stirring.

Preparation of Curing Agents of Examples 2 to 6 and Comparative Examples 1 to 5 Examples 2 to 5 and Comparative Examples 1 to 5 were prepared in the same procedure as in the preparation of the curing agent of Example 1 at the compounding ratios shown in Tables 1 and 2. 3 curing agents were prepared.
Piperidine is a secondary amine compound. The molar ratio of the epoxy group / the reactive group of the curing agent in Examples 1 to 6 and Comparative Examples 1 to 5 is 1 / 0.5 to 1/2.

Two-component mixing method The main agent and the curing agent were weighed so as to have a weight ratio of 1: 1, 3% of the total amount of water was added, and the mixture was mixed for 2 minutes until uniform. In Comparative Example 4, (number of moles of epoxy group / number of moles of curing agent) = 1 / 0.5, the main agent and the curing agent were stirred at a weight ratio of 1: 2.
Using this two-component mixture, test pieces for confirming the initial curing time, shear strength, and peel strength were prepared.

Initial curing time The initial curing time was confirmed using a JIS K6253 Type A hardness tester.
The above two-component mixture immediately after mixing was smoothly applied to a thickness of 12 mm in an atmosphere of 23 ° C., and the time until the type A hardness reached 80 was measured. The results are shown in Tables 3 and 4. As a criterion, pass within 60 minutes and fail over 60 minutes.
In Comparative Example 4 and Comparative Example 5 which failed in the initial curing time, the shear strength and the peel strength were not measured.

Shear strength In order to confirm the adhesive strength to hard vinyl chloride, a shear strength test was conducted using commercially available hard vinyl chloride. Two commercially available hard vinyl chloride plates having a thickness of 100 mm × 25 mm × 5 mm were prepared, and the above two-component mixture was applied to one of them with a spatula of about 0.2 g so that the adhesive area became 25 mm × 12.5 mm. Put another hard vinyl chloride plate on top of each other, place it on a weight so that a pressure of 0.05 MPa is evenly applied, store it in an environment of 23 ° C for 8 hours, and cut off the part where the cured product protrudes with a cutter. It was used as an adhesive strength test piece.
The shear test conditions are a tensile speed of 10 mm / min under an environment of 23 ° C. The results are shown in Tables 3 and 4.
Below the shear strength, the fracture mode is shown, AF is interfacial fracture, CF is cohesive fracture, and MF is material fracture. As a criterion, regarding the shear strength, 4 MPa or more is acceptable, and less than 4 MPa is unacceptable. Regarding the destruction mode, CF and MF pass, and AF fails.

Peel strength A 90 ° peel strength test of a commercially available hard vinyl chloride plate and a thin aluminum plate was performed on the assumption that the PVC pipe was deformed by external stress.
A commercially available hard vinyl chloride plate having a thickness of 100 mm × 25 mm × 5 mm and A1100 which is aluminum having a thickness of 100 mm × 25 mm × 0.5 mm were prepared.
About 1 g of the above two-component mixture was thinly stretched and applied to a commercially available hard vinyl chloride plate with a spatula, and the A1100 plates were superposed so that the adhesive area was 25 mm × about 70 mm. It was placed on a weight so that a pressure of 0.2 MPa was uniformly applied, and stored in an environment of 23 ° C. for 8 hours. The portion where the cured product protruded was cut off with a cutter to prepare an adhesive strength test piece.
A 90 ° peel test was performed by fixing a hard vinyl chloride plate to a 90 ° peel jig with double-sided tape and sandwiching a portion of the aluminum plate without a cured product with an air chuck. The 90 ° peel test condition is a tensile speed of 200 mm / min in an environment of 23 ° C. The results are shown in Tables 3 and 4.
Below the peel strength, the fracture mode is shown, AF is interfacial fracture, CF is cohesive fracture, and MF is material fracture. As a criterion, regarding the peel strength, 65N / 25mm or more is acceptable, and less than 65N / 25mm is unacceptable. Regarding the destruction mode, CF and MF pass, and AF fails.

5 to 90% by weight of bisphenol epoxy compound as main agent, 0.1 to 50% by weight of thiol compound as curing agent, 0.1 to 50% by weight of tertiary amine, amino group terminal nitrile- Examples 1 to 6 contain 0.1 to 50% by weight of butadiene rubber (: ATBN) and the amount of ATBN is smaller than that of the bisphenol epoxy resin. Examples 1 to 6 include initial curing time, shear strength, peel strength and Both the destruction modes passed.

In Comparative Example 1 containing no thiol compound and Comparative Example 2 containing no tertiary amine, the shear strength was acceptable, but the peel strength and the initial curing time were unacceptable. It has been shown that thiol compounds and tertiary amines are essential components.

In Comparative Example 3 containing no ATBN, the shear strength and the initial curing time were acceptable, but the peel strength was unacceptable.
Comparative Example 4, in which the amount of ATBN added was larger than that of the bisphenol epoxy compound, was rejected at the initial curing time. ATBN is an essential component, but when the amount exceeds a certain range, it has been shown to be unsuitable as an epoxy resin composition for adhering to a rigid vinyl chloride pipe.

Comparative Example 5 in which the secondary amine piperidine was used instead of the tertiary amine was rejected at the initial curing time. It has been shown that secondary amines cannot substitute for tertiary amines.

Claims (2)

An epoxy resin composition for adhering to a hard vinyl chloride tube. The main agent is 5 to 90% by weight of the bisphenol epoxy compound, and the curing agent is 0.1 to 50% by weight of the thiol compound, and the tertiary amine is the whole. Contains 0.1 to 50% by weight of amino group-terminated nitrile-butadiene rubber (: ATBN), and 0.1 to 50% by weight of the total.
Moreover, ATBN is an epoxy resin composition for adhering to a rigid vinyl chloride pipe, which is in a smaller amount than the bisphenol-based epoxy compound. A rigid vinyl chloride pipe joined by using the epoxy resin composition according to claim 1.