JP6908812B2 - Epoxy group-terminated polysulfide polymer - Google Patents

Description

The present invention relates to epoxy group-terminated polysulfide polymers. In particular, the present invention relates to an epoxy group-terminated polysulfide polymer having good storage stability and good heat resistance.

The mercaptan-terminated polysulfide polymer has a thiol group at the terminal and is easily oxidized and cured by an oxidizing agent such as lead dioxide or manganese dioxide. The rubber-like cured product obtained by curing the polysulfide polymer contains sulfur in the main chain of the molecule and does not contain double bonds, so it has excellent oil resistance, weather resistance, watertightness, and airtightness. It is widely used as a sealant, an adhesive and a paint because of its high adhesive strength.

However, the mercaptan-terminated polysulfide polymer has an odor due to the mercaptan group at the terminal, and has a problem that its use and place of use are restricted. An epoxy group-terminated polysulfide polymer has been developed to solve this problem. Epoxy group-terminated polysulfide polymers have been widely used because of their high adhesive strength, chemical resistance, durability, impact resistance, and gas barrier properties (see Patent Documents 1 and 2).

However, the conventional epoxy group-terminated polysulfide polymer has poor storage stability and a large increase in viscosity over time. Therefore, there is a problem that the viscosity increases after production and long-term storage is not possible. Further, conventional sealants and adhesives using epoxy group-terminated polysulfide polymers have a problem of poor storage stability.

Special Fair 01-000411 Gazette Japanese Unexamined Patent Publication No. 06-116387

The present invention provides an epoxy group-terminated polysulfide polymer having good storage stability and good heat resistance.

The epoxy group-terminated polysulfide polymer of the present invention has the following general formula.

(However, a, b, and c are independent integers of 0 or 1 to 50, the total of a + b + c is 3 to 50, d is an integer of 1 to 3, and X is an integer of 1 to 5. Yes, R ¹ is the following general formula
_{-C 2 H 4 -O-C 2} H 4 -O-C 2 H 4 -
It is an organic group represented by, and R ² , R ³ , and R ⁴ are independent of each other and have the following general formulas.

It is an organic group represented by, R ⁶ is H or CH ₃ , and e is 0 to 3. ) Is an epoxy group-terminated polysulfide polymer.

The epoxy group-terminated polysulfide polymer of the present invention has better storage stability than the conventional epoxy group-terminated polysulfide polymer, and its viscosity does not increase even after long-term storage. Further, the epoxy group-terminated polysulfide polymer of the present invention has good heat resistance.

The cured product obtained by curing the epoxy group-terminated polysulfide polymer of the present invention with a curing agent has high flexibility, excellent water resistance, chemical resistance, and weather resistance, and further has high adhesive strength. The cured product obtained by curing the epoxy group-terminated polysulfide polymer of the present invention with a curing agent can be used as an adhesive, a sealing material, a potting material, a coating material, a resin modifier, a primer and the like.

The epoxy group-terminated polysulfide polymer of the present invention is, in particular, a civil engineering / building adhesive, a civil engineering / building coating material, a civil engineering / building primer, an electric / electronic adhesive, an electric / electronic potting material, and a vehicle adhesive. , Can be used as a vehicle primer.

Hereinafter, the present invention will be described in detail.

The epoxy group-terminated polysulfide polymer of the present invention is an epoxy group-terminated polysulfide polymer represented by the following general formula (1).

R ¹ is the following general formula
_{-C 2 H 4 -O-C 2} H 4 -O-C 2 H 4 -
It is an organic group indicated by.

In the epoxy group-terminated polysulfide polymer of the present invention, a, b, and c are independent of each other and are integers of 0 or 1 to 50, and the total of a, b, and c is 3 to 50. When the total of a, b, and c is larger than 50, the viscosity of the epoxy group-terminated polysulfide polymer becomes high, which makes it difficult to produce the epoxy group-terminated polysulfide polymer. Further, when the total of a, b, and c is larger than 50, the viscosity of the epoxy group-terminated polysulfide polymer is high. Therefore, the epoxy group-terminated polysulfide polymer is modified for an adhesive, a sealing material, a potting material, a coating material, and a resin. It is difficult to use as a material and primer.

In the epoxy group-terminated polysulfide polymer of the present invention, d is an integer of 1 to 3. When d is larger than 3, the viscosity of the epoxy group-terminated polysulfide polymer increases, which makes it difficult to produce the epoxy group-terminated polysulfide polymer. Further, when d is larger than 3, the viscosity of the epoxy group-terminated polysulfide polymer is high, so that the epoxy group-terminated polysulfide polymer can be used as an adhesive, a sealing material, a potting material, a coating material, a resin modifier, a primer, or the like. , Difficult to use.

The epoxy group-terminated polysulfide polymer of the present invention has an X of 1 to 5. The epoxy group-terminated polysulfide polymer of the present invention preferably has an average value of x of 1 to 2.5. The average value of x is more preferably 1.1 to 2.0, even more preferably 1.1 to 1.9, and even more preferably 1.1 to 1.8. In particular, when the average value of x is preferably 1.1 to 1.9, more preferably 1.1 to 1.8, the epoxy group-terminated polysulfide having low viscosity, low glass transition temperature, and high heat resistance. A polymer is obtained.

In the epoxy group-terminated polysulfide polymer of the present invention, R ² , R ³ , and R ⁴ are independent of each other and have the following general formula.

It is an organic group represented by, R ⁶ is H or CH ₃ , and e is 0 to 3.

The weight average molecular weight of the epoxy group-terminated polysulfide polymer of the present invention is preferably 1000 to 10000, and more preferably 1000 to 8000.

The epoxy group-terminated polysulfide polymer of the present invention has an epoxy equal amount of preferably 200 to 5000, more preferably 200 to 4000.

The epoxy group-terminated polysulfide polymer of the present invention preferably contains 1 to 6 epoxy groups in one molecule, and more preferably contains 3 to 5 epoxy groups in one molecule.

The epoxy group-terminated polysulfide polymer of the present invention can be produced by reacting a mercaptan-terminated polysulfide polymer with a bisphenol F-type epoxy resin or a bisphenol A-type epoxy resin. The mercaptan-terminated polysulfide polymer used in the reaction may be a liquid polysulfide polymer produced via solid polysulfide, or a liquid polysulfide polymer produced without the formation of solid polysulfide.

The bisphenol A type epoxy resin for producing the epoxy group-terminated polysulfide polymer of the present invention has an epoxy equal amount of preferably 170 to 3000, and more preferably 170 to 600.

The bisphenol A type epoxy resin for producing the epoxy group-terminated polysulfide polymer of the present invention has a viscosity of preferably 1 Pa · s to 200 Pa · s, and more preferably 1 Pa · s to 50 Pa · s.

The bisphenol A type epoxy resin for producing the epoxy group-terminated polysulfide polymer of the present invention has a molecular weight of preferably 320 to 6000, and more preferably 320 to 1200.

The mercaptan-terminated polysulfide polymer for producing the epoxy group-terminated polysulfide polymer of the present invention has a viscosity of preferably 0.1 Pa · s to 150 Pa · s, more preferably 0.1 Pa · s to 20 Pa · s. Is.

The epoxy group-terminated polysulfide polymer of the present invention can be mixed with a bisphenol F type epoxy resin or a bisphenol A type epoxy resin in an arbitrary ratio.

The bisphenol A type epoxy resin mixed with the epoxy group-terminated polysulfide polymer of the present invention has a viscosity of preferably 1 Pa · s to 200 Pa · s, and more preferably 1 Pa · s to 50 Pa · s.

The bisphenol A type epoxy resin to be mixed with the epoxy group-terminated polysulfide polymer of the present invention has an epoxy equal amount of preferably 170 to 3000, more preferably 170 to 600.

The bisphenol A type epoxy resin to be mixed with the epoxy group-terminated polysulfide polymer of the present invention has a molecular weight of preferably 320 to 6000, more preferably 320 to 1200.

In the epoxy group-terminated polysulfide polymer of the present invention, it is preferable to mix 25 to 400 parts by weight of a bisphenol F type epoxy resin with 100 parts by weight of the epoxy group-terminated polysulfide polymer. By mixing 45 to 400 parts by weight of the bisphenol F type epoxy resin with 100 parts by weight of the epoxy group-terminated polysulfide polymer, a cured product having high hardness and flexibility can be obtained. The mixing amount of the bisphenol F type epoxy resin with respect to 100 parts by weight of the epoxy group-terminated polysulfide polymer is more preferably 33 to 300 parts by weight, and even more preferably 42 to 233 parts by weight.

In the epoxy group-terminated polysulfide polymer of the present invention, it is preferable to mix 25 to 400 parts by weight of a bisphenol A type epoxy resin with 100 parts by weight of the epoxy group-terminated polysulfide polymer. By mixing 33 to 400 parts by weight of the bisphenol A type epoxy resin with 100 parts by weight of the epoxy group-terminated polysulfide polymer, a cured product having high hardness and flexibility can be obtained. The mixing amount of the bisphenol A type epoxy resin with respect to 100 parts by weight of the epoxy group-terminated polysulfide polymer is more preferably 45 to 300 parts by weight, and even more preferably 45 to 233 parts by weight.

The epoxy group-terminated polysulfide polymer of the present invention can be further mixed with a bisphenol F type epoxy resin or a bisphenol A type epoxy resin, and a reactive diluent. Reactive diluents include butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, sec-butylphenol glycidyl ether, glycidol, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, polypropylene glycol di. Examples thereof include glycidyl ether and ethylene glycol diglycidyl ether.

As the curing agent for curing the epoxy group-terminated polysulfide polymer of the present invention, a curing agent for curing a bisphenol F type epoxy resin or a bisphenol A type epoxy resin can be used. The curing agent for curing the epoxy group-terminated polysulfide polymer of the present invention includes, for example, aliphatic diamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, trimethylenediamine, hexamethylenediamine, and tetramethylenediamine, and metaxylene diamines. Aromatic diamines such as diaminodisenylmethane, diaminodiphenylsulfone, metaphenylenediamine, aliphatic tertiary amines such as N, N-dimethylpropylamine, N, N, N', N'-tetramethylhexamethylenediamine, Alicyclic tertiary amines such as N-methylpiperidin and N, N'-dimethylpiperazin, aromatic tertiary amines such as benzyldimethylamine, dimethylaminomethylphenol, and 2,4,6-tris (dimethylaminomethyl) phenol. With amines, polyamine epoxy resin adducts produced by reacting epoxy resins with excess amines, polyamine-ethylene oxide adducts, polyamine-propylene oxide adducts, cyanoethylated polyamines, diamines whose main chain is silicon, or polyamines. Modified polyamines such as dehydration condensates obtained by reacting phenols and aldehydes, imidazoles such as 2-ethyl-4-methylimidazole, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydro Examples thereof include acid anhydrides such as phthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and trimellitic anhydride. As a curing agent for curing the epoxy group-terminated polysulfide polymer of the present invention, a modified aliphatic polyamine such as Daitoclar X-2392 or Daitoclar X-7906 manufactured by Daito Sangyo Co., Ltd. can be used.

As the curing agent for curing the mixture of the epoxy group-terminated polysulfide polymer of the present invention and the bisphenol F type epoxy resin or the bisphenol A type epoxy resin, a curing agent for curing the bisphenol F type epoxy resin or the bisphenol A type epoxy resin is used. be able to. The curing agent for curing the mixture of the epoxy group-terminated polysulfide polymer of the present invention and the bisphenol F type epoxy resin or bisphenol A type epoxy resin is, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, trimethylenediamine, hexa. Aliper diamines such as methylenediamine and tetramethylenediamine, aromatic diamines such as metaxylene diamine, diaminodisenylmethane, diaminodiphenylsulfone and metaphenylenediamine, N, N-dimethylpropylamine, N, N, N', N Aliper tertiary amines such as'-tetramethylhexamethylenediamine, alicyclic tertiary amines such as N-methylpiperidin, N, N'-dimethylpiperazine, benzyldimethylamine, dimethylaminomethylphenol, 2,4 , 6-Tris (dimethylaminomethyl) phenol and other aromatic tertiary amines, polyamine epoxy resin adduct produced by reacting epoxy resin with excess amine, polyamine-ethylene oxide adduct, polyamine-propylene oxide adduct, cyanoethyl Polyamines formed, diamines having a main chain of silicon, or modified polyamines such as dehydration condensates obtained by reacting polyamines with phenols and aldehydes, and imidazoles such as 2-ethyl-4-methylimidazole. Examples thereof include acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and trimellitic anhydride. As a curing agent for curing a mixture of the epoxy group-terminated polysulfide polymer of the present invention and a bisphenol F type epoxy resin or a bisphenol A type epoxy resin, Daito Sangyo Co., Ltd., Daitokuraru X-2392 or Daitokuraru X-7906, etc. Denatured aliphatic polyamines can be used.

The present invention will be described in more detail with reference to the following examples.

Viscosity measurement Viscosity was measured at 25 ° C. using a viscometer U-EII manufactured by Toki Sangyo.

Gel Permeation Chromatography Analysis, Measurement of Weight Average Molecular Weight (Mw) The column used was TSKgelG3000HXL, TSKgelG2000HXL, and TSKgelG1000HXL connected in series, and the detector was MODEL504R RI Detector manufactured by GL Science Co., Ltd. And Hitachi Co., Ltd. L-D4000 UV Detector was used. A sample was dissolved in THF (tetrahydrofuran) to prepare a 1% THF (tetrahydrofuran) solution, which was measured at a column temperature of 40 ° C. using THF (tetrahydrofuran) having a flow rate of 1.0 ml / min as a mobile phase. As for the molecular weight, the weight average molecular weight (Mw) was measured using polyethylene glycol as a standard and the GPC data processing software SIC480II data station manufactured by Shoko Scientific Co., Ltd.

Measurement of SH content The sample was dissolved in a mixed solution of toluene and pyridine, an aqueous potassium iodide solution was added, and then titration was performed using an iodine standard solution.

Measurement of Epoxy Equivalent 0.2 g of a sample was weighed in a beaker, 10 ml of toluene and 20 ml of acetic acid were added, and the mixture was stirred and dissolved. To this, 10 ml of a tetraethylammonium bromide acetic acid solution was added and stirred, and 2 to 3 drops of a crystal violet indicator solution was further added. Titration was performed using a 0.1 mol / L acetic acid perchlorate solution, and the titration amount was read with the point where the color of the sample solution began to turn green as the end point. Epoxy equivalent is calculated by the following formula: Epoxy equivalent = {1000 x sample weight (g)} / {0.1 x titer (ml) x titer}
Calculated.

Measurement of stability when stored at 50 ° C. The sample was stored in a constant temperature bath at 50 ° C., and the change in viscosity over time was measured.

Measurement of hardness A modified aliphatic polyamine (Diteclar X-2392 or Daitoclar X-7906 manufactured by Daito Sangyo Co., Ltd.) was used as a curing agent. A sample of a mixture of an epoxy group-terminated polysulfide polymer and a modified aliphatic polyamine (Diteclar X-2392 or Diteclar X-7906 manufactured by Daito Sangyo Co., Ltd.) was placed in a polypropylene cup and placed in a polypropylene cup at 23 ° C. for 5 days in a 50% RH atmosphere. It was cured. After the cured sample is removed from the polypropylene cup and the surface is smoothed with a metal file, a "digital rubber hardness tester DD2-D type" manufactured by Polymer Meter Co., Ltd. is used in an atmosphere of 23 ° C. The "D hardness" value of was measured and recorded.

Measurement of repellent A modified aliphatic polyamine (Diteclar X-2392 or Daitoclar X-7906 manufactured by Daito Sangyo Co., Ltd.) was used as a curing agent. A sample obtained by mixing an epoxy group-terminated polysulfide polymer and a modified aliphatic polyamine (Diteclar X-2392 or Diteclar X-7906 manufactured by Daito Sangyo Co., Ltd.) was applied to a hot-dip galvanized steel sheet to a thickness of 120 μm using a bar coater. .. After curing for 5 days in a 50% RH atmosphere at 23 ° C., the surface was visually observed to measure the presence or absence of cissing. Samples with less than 6 repellents with a diameter of 1 mm or more were judged as ◯ (good), and samples with 6 or more repellents were judged as × (poor).

Measurement of flex resistance As a curing agent, a modified aliphatic polyamine (Diteclar X-2392 or Daitoclar X-7906 manufactured by Daito Sangyo Co., Ltd.) was used. A sample obtained by mixing an epoxy group-terminated polysulfide polymer and a modified aliphatic polyamine (Diteclar X-2392 or Diteclar X-7906 manufactured by Daito Sangyo Co., Ltd.) was applied to a hot-dip galvanized steel sheet to a thickness of 120 μm using a bar coater. .. After curing for 5 days in a 50% RH atmosphere at 23 ° C., bending resistance was measured according to JIS K 5600-5-1 using a mandrel having a diameter of 2 mm. A sample in which cracks and peeling were not observed at the bent portion of the coating film was evaluated as ◯ (good), and a sample in which cracks and peeling were observed was evaluated as × (defective).

Measurement of heat resistance The sample was measured for weight loss by heating in a nitrogen atmosphere with a thermogravimetric analyzer (TGA-Q50 manufactured by TA Instruments). The temperature rise was 10 ° C./min.

Synthesis of mercaptan-terminated polysulfide polymer Synthesis example 1
482.1 g of polysodium sulfide aqueous solution (2.06 mol / L), 1.9 g of tetrabutylammonium bromide 50 wt% aqueous solution, 1,2-bis (2-chloroethoxy) ethane 224.5 g, 1 in a 2 L four-necked flask. , 2,3-Trichloropropane (2.4 g) was charged and reacted at 80 ° C. for 4 hours with mixing and stirring. Then, 276.2 g of 15.6 wt% sodium sulfite and 53.8 g of a 46% aqueous sodium hydrosulfide solution were added, and after further reacting at 80 ° C. for 4 hours, water was removed to obtain a pale yellow transparent liquid polysulfide polymer. The obtained polymer had a viscosity of 730 mPa · s, a weight average molecular weight (Mw) of 1500 by gel permeation chromatography, and an SH content of 6.8% by weight.

Synthesis example 2
482.1 g of polysodium sulfide aqueous solution (2.06 mol / L), 3.9 g of tetrabutylammonium bromide 50 wt% aqueous solution, 1,2-bis (2-chloroethoxy) ethane 224.5 g, 1 in a 2 L four-necked flask. , 2,3-Trichloropropane (44.2 g) was charged and reacted at 80 ° C. for 4 hours with mixing and stirring. Then, 439.2 g of 15.6 wt% sodium sulfite and 206.7 g of a 46% aqueous sodium hydrosulfide solution were added, and after further reacting at 80 ° C. for 4 hours, water was removed to obtain a pale yellow transparent liquid polysulfide polymer. The obtained polymer had a viscosity of 180 mPa · s, a weight average molecular weight (Mw) of 880 by gel permeation chromatography, and an SH content of 15.4% by weight.

Synthesis example 3
553.1 g of polysodium sulfide aqueous solution (2.06 mol / L), 3.9 g of tetrabutylammonium bromide 50 wt% aqueous solution, 1,2-bis (2-chloroethoxy) ethane 224.5 g, 1 in a 2 L four-necked flask. , 2,3-Trichloropropane (3.0 g) was charged and reacted at 80 ° C. for 4 hours with mixing and stirring. Then, 321.7 g of 15.6 wt% sodium sulfite and 13.5 g of a 46% aqueous sodium hydrosulfide solution were added, and after further reacting at 80 ° C. for 4 hours, water was removed to obtain a pale yellow transparent liquid polysulfide polymer. The obtained polymer had a viscosity of 1220 mPa · s, a weight average molecular weight (Mw) of 5100 by gel permeation chromatography, and an SH content of 2.3% by weight.

Synthesis example 4
482.1 g of polysodium sulfide aqueous solution (2.06 mol / L), 1.9 g of tetrabutylammonium bromide 50 wt% aqueous solution, 207.6 g of bis (2-chloroethyl) formal, 1,2,3- in a 2 L four-necked flask. 2.4 g of trichloropropane was charged and reacted at 80 ° C. for 4 hours with mixing and stirring. Then, 439.2 g of 15.6 wt% sodium sulfite and 53.8 g of a 46% aqueous sodium hydrosulfide solution were added, and after further reacting at 80 ° C. for 4 hours, water was removed to obtain a pale yellow transparent liquid polysulfide polymer. The obtained polymer had a viscosity of 1060 mPa · s, a weight average molecular weight (Mw) of 5100 by gel permeation chromatography, and an SH content of 6.8% by weight.

Synthesis example 5
553.1 g of polysodium sulfide aqueous solution (2.06 mol / L), 3.9 g of tetrabutylammonium bromide 50 wt% aqueous solution, 207.6 g of bis (2-chloroethyl) formal, 1,2,3- in a 2 L four-necked flask. 3.0 g of trichloropropane was charged and reacted at 80 ° C. for 4 hours with mixing and stirring. Then, 321.7 g of 15.6 wt% sodium sulfite and 13.5 g of a 46% aqueous sodium hydrosulfide solution were added, and after further reacting at 80 ° C. for 4 hours, water was removed to obtain a pale yellow transparent liquid polysulfide polymer. The obtained polymer had a viscosity of 1600 mPa · s, a weight average molecular weight (Mw) of 5600 by gel permeation chromatography, and an SH content of 2.5% by weight.

Synthesis of Epoxy Group-Terminal Polysulfide Polymer Example 1
69 parts by weight of bisphenol F type epoxy resin (jER807 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170) was charged to 100 parts by weight of the polymer of Synthesis Example 1 in a 1 L four-necked flask, and the mixture was mixed and stirred at 80 ° C. The reaction was carried out until the SH content was 0.2% or less to obtain a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol F type epoxy resin at 80/20 (weight ratio). The viscosity of the obtained mixture was 95 Pa · s and the epoxy equivalent was 807. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 4400.

Example 2
125.5 parts by weight of bisphenol F type epoxy resin (jER807 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170) was charged to 100 parts by weight of the polymer of Synthesis Example 1 in a 1 L 4-port flask, and mixed and stirred at 70 ° C. While reacting until the SH content was 0.2% or less, a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol F type epoxy resin was obtained at 60/40 (weight ratio). The viscosity of the obtained mixture was 51 Pa · s and the epoxy equivalent was 403. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 3200.

Example 3
170.6 parts by weight of bisphenol F type epoxy resin (jER807 manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 170) was charged to 100 parts by weight of the polymer of Synthesis Example 1 in a 1 L four-necked flask at 70 ° C. The reaction was carried out with mixing and stirring until the SH content value became 0.2% or less to obtain a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol F type epoxy resin in a 50/50 (weight ratio). The viscosity of the obtained mixture was 17 Pa · s and the epoxy equivalent was 314. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 2200.

Using a mixture of the epoxy group-terminated polysulfide polymer of Example 3 and the bisphenol F type epoxy resin at 50/50 (weight ratio), the viscosities were measured after 15, 30, 45, and 60 days after storage at 50 ° C. .. The results are shown in Table 1.

Using a polymer mixture of the epoxy group-terminated polysulfide polymer of Example 3 and the bisphenol F type epoxy resin at 50/50 (weight ratio), the weight loss% by heating at 150 ° C., 200 ° C., and 250 ° C. was measured. The results are shown in Table 2.

Comparative Example 1
170.6 parts by weight of bisphenol F type epoxy resin (jER807 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170) was charged to 100 parts by weight of the polymer of Synthesis Example 4 in a 1 L 4-port flask, and mixed and stirred at 80 ° C. While reacting until the SH content was 0.2% or less, a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol F type epoxy resin was obtained at 50/50 (weight ratio). The viscosity of the obtained mixture was 22 Pa · s and the epoxy equivalent was 322. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 2500.

Using a mixture of the epoxy group-terminated polysulfide polymer of Comparative Example 1 and the bisphenol F type epoxy resin at 50/50 (weight ratio), 15 days, 30 days, and 45 days after storage at 50 ° C. in the same manner as in Example 3, The viscosity after 60 days was measured. The results are shown in Table 1.

Weight by heating at 150 ° C., 200 ° C., 250 ° C. using a mixture of the epoxy group-terminated polysulfide polymer of Comparative Example 1 and the bisphenol F type epoxy resin at 50/50 (weight ratio) in the same manner as in Example 3. The% weight loss was measured and the results are shown in Table 2.

As shown in Table 1, it was shown that the mixture of the epoxy group-terminated polysulfide polymer of the present invention and the bisphenol F type epoxy resin is a stable polymer with almost no change in viscosity even after storage at 50 ° C. for 60 days. The viscosity of the mixture of the epoxy group-terminated polysulfide polymer of Comparative Example 1 and the bisphenol F type epoxy resin increased significantly when stored at 50 ° C. for 60 days.

Example 4
179.3 parts by weight of a bisphenol F type epoxy resin (jER807 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170) is mixed with 100 parts by weight of the polymer of Synthesis Example 3 in a 1 L four-necked flask, and at 60 ° C. The mixture was reacted with mixing and stirring until the SH content became 0.2% or less to obtain a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol F type epoxy resin at 40/60 (weight ratio). The viscosity of the obtained mixture was 13 Pa · s and the epoxy equivalent was 270. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 5100.

Using a polymer mixture of 40/60 (weight ratio) of the epoxy group-terminated polysulfide polymer of Example 4 and the bisphenol F type epoxy resin, the weight loss% by heating at 150 ° C., 200 ° C., and 250 ° C. was measured. The results are shown in Table 2.

As shown in Table 2, the mixture of the epoxy group-terminated polysulfide polymer and the bisphenol F type epoxy resin of the present invention is compared with the mixture of the epoxy group-terminated polysulfide polymer of Comparative Example 1 and the bisphenol F type epoxy resin at each temperature. It was shown that the weight loss rate was small and there was little thermal decomposition at high temperature heating.

Example 5
259.0 parts by weight of a bisphenol F type epoxy resin (jER807 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170) was charged to 100 parts by weight of the polymer of Synthesis Example 2 in a 1 L four-necked flask, and at 50 ° C. The reaction was carried out with mixing and stirring until the SH content became 0.2% or less to obtain a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol F type epoxy resin in a 50/50 (weight ratio). The viscosity of the obtained mixture was 134 Pa · s and the epoxy equivalent was 328. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture was 2900 by gel permeation chromatography.

Example 6
86.2 parts by weight of bisphenol F type epoxy resin (jER807 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170) was mixed with 100 parts by weight of the polymer of Synthesis Example 3 in a 1 L 4-necked flask and mixed at 70 ° C. The reaction was carried out with stirring until the SH content became 0.2% or less to obtain a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol F type epoxy resin in a ratio of 60/40 (weight ratio). The viscosity of the obtained mixture was 29 Pa · s and the epoxy equivalent was 410. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by GPC was 6500.

Example 7
132.2 parts by weight of bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) was charged to 100 parts by weight of the polymer of Synthesis Example 1 in a 1 L four-necked flask, and mixed and stirred at 70 ° C. While reacting until the SH content was 0.2% or less, a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol A type epoxy resin was obtained at 60/40 (weight ratio). The viscosity of the obtained mixture was 68 Pa · s and the epoxy equivalent was 491. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 2900.

Using a mixture of the epoxy group-terminated polysulfide polymer of Example 7 and the bisphenol A type epoxy resin at 60/40 (weight ratio), the viscosities were measured 60 days and 80 days after storage at 50 ° C. The results are shown in Table 3.

Using a polymer mixture of the epoxy group-terminated polysulfide polymer of Example 7 and the bisphenol A type epoxy resin at 60/40 (weight ratio), the weight loss% by heating at 150 ° C., 200 ° C., and 250 ° C. was measured. The results are shown in Table 4.

Example 8
248 parts by weight of a bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) is charged to 100 parts by weight of the polymer of Synthesis Example 1 in a 1 L four-necked flask, and mixed and stirred at 70 ° C. While reacting until the SH content was 0.2% or less, a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol A type epoxy resin was obtained at 40/60 (weight ratio). The viscosity of the obtained mixture was 33 Pa · s and the epoxy equivalent was 311. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 2300.

Using a mixture of the epoxy group-terminated polysulfide polymer of Example 8 and the bisphenol A type epoxy resin at 40/60 (weight ratio), the viscosities were measured 60 days and 80 days after storage at 50 ° C. The results are shown in Table 3.

Comparative Example 2
178.6 parts by weight of bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) was charged to 100 parts by weight of the polymer of Synthesis Example 4 in a 1 L four-necked flask, and mixed and stirred at 80 ° C. While reacting until the SH content was 0.2% or less, a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol A type epoxy resin was obtained at 50/50 (weight ratio). The viscosity of the obtained mixture was 54 Pa · s and the epoxy equivalent was 356. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 2200.

Using a mixture of the epoxy group-terminated polysulfide polymer of Comparative Example 2 and the bisphenol A type epoxy resin at 50/50 (weight ratio), the viscosities were measured 60 days and 80 days after storage at 50 ° C. in the same manner as in Example 7. did. The results are shown in Table 3.

Weight loss by heating at 150 ° C., 200 ° C., and 250 ° C. using a mixture of the epoxy group-terminated polysulfide polymer of Comparative Example 2 and the bisphenol A type epoxy resin at 50/50 (weight ratio) in the same manner as in Example 7. % Is measured and the results are shown in Table 4.

As shown in Table 3, the mixture of the epoxy group-terminated polysulfide polymer of the present invention and the bisphenol A type epoxy resin was shown to be a stable polymer with almost no change in viscosity even after storage at 50 ° C. for 80 days. The mixture of the epoxy group-terminated polysulfide polymer of Comparative Example 2 and the bisphenol A type epoxy resin greatly increased in viscosity when stored at 50 ° C. for 60 days, and gelled on the 80th day, making it impossible to measure the viscosity.

Example 9
276.8 parts by weight of a bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) was mixed with 100 parts by weight of the polymer of Synthesis Example 2 in a 1 L four-necked flask, and at 60 ° C. The reaction was carried out with mixing and stirring until the SH content became 0.2% or less to obtain a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol A type epoxy resin in a 50/50 (weight ratio). The viscosity of the obtained mixture was 172 Pa · s and the epoxy equivalent was 390. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 3100.

Using a polymer mixture of the epoxy group-terminated polysulfide polymer of Example 9 and the bisphenol A type epoxy resin at 50/50 (weight ratio), the weight loss% by heating at 150 ° C., 200 ° C., and 250 ° C. was measured. The results are shown in Table 4.

Example 10
182.5 parts by weight of a bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) was charged to 100 parts by weight of the polymer of Synthesis Example 3 in a 1 L four-necked flask at 50 ° C. The reaction was carried out with mixing and stirring until the SH content became 0.2% or less to obtain a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol A type epoxy resin at 40/60 (weight ratio). The viscosity of the obtained mixture was 25 Pa · s and the epoxy equivalent was 297. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 5200.

Using a polymer mixture of the epoxy group-terminated polysulfide polymer of Example 10 and the bisphenol A type epoxy resin at 50/50 (weight ratio), the weight loss% by heating at 150 ° C., 200 ° C., and 250 ° C. was measured. The results are shown in Table 4.

Comparative Example 3
182.6 parts by weight of bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) was charged to 100 parts by weight of the polymer of Synthesis Example 5 in a 1 L four-necked flask, and mixed and stirred at 70 ° C. While reacting until the SH content was 0.2% or less, a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol A type epoxy resin was obtained at 40/60 (weight ratio). The viscosity of the obtained mixture was 32 Pa · s and the epoxy equivalent was 313. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 5500.

Using a mixture of the epoxy group-terminated polysulfide polymer of Comparative Example 3 and the bisphenol A type epoxy resin at 40/60 (weight ratio), the weight by heating at 150 ° C., 200 ° C., and 250 ° C. in the same manner as in Example 7. The% weight loss was measured and the results are shown in Table 4.

As shown in Table 4, the epoxy group-terminated polysulfide polymer bisphenol A type epoxy resin mixture of the present invention is compared with the epoxy group-terminated polysulfide polymer bisphenol A type epoxy resin mixture of Comparative Example 2 and Comparative Example 3 at each temperature. It was shown that the weight loss rate by heating was small and the thermal decomposition by high temperature heating was small.

Example 11
88.3 parts by weight of bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) was mixed with 100 parts by weight of the polymer of Synthesis Example 3 in a 1 L four-necked flask and mixed at 70 ° C. The reaction was carried out with stirring until the SH content became 0.2% or less to obtain a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol A type epoxy resin at 60/40 (weight ratio). The viscosity of the obtained mixture was 45 Pa · s and the epoxy equivalent was 469. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 6200.

Example 12
41.2 parts by weight of bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 190) was mixed with 100 parts by weight of the polymer of Synthesis Example 3 in a 1 L four-necked flask and mixed at 80 ° C. The reaction was carried out with stirring until the SH content became 0.2% or less to obtain a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol A type epoxy resin at 80/20 (weight ratio). The viscosity of the obtained mixture was 88 Pa · s and the epoxy equivalent was 775. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 7600.

Example 13
74 parts by weight of bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) was charged to 100 parts by weight of the polymer of Synthesis Example 1 in a 1 L four-necked flask, and the mixture was mixed and stirred at 80 ° C. The reaction was carried out until the SH content was 0.2% or less to obtain a mixture of the epoxy group-terminated polysulfide polymer and the bisphenol A type epoxy resin at 80/20 (weight ratio). The viscosity of the obtained mixture was 143 Pa · s and the epoxy equivalent was 895. The weight average molecular weight (Mw) of the epoxy group-terminated polysulfide polymer in the mixture by gel permeation chromatography was 4700.

Examples 14-19
A curing agent (Daitoclar X-2392 manufactured by Daito Sangyo Co., Ltd.) was added to the mixture of the epoxy group-terminated polysulfide polymer of Examples 1 to 6 and the bisphenol F type epoxy resin. The mixture was mixed so that the ratio was 1: 1 and the mixture was mixed and stirred. The mixing ratio of the mixture of the epoxy group-terminated polysulfide polymer and the bisphenol F type epoxy resin and the curing agent is shown in Table 5. After curing for 5 days in a 23 ° C. and 50% RH atmosphere, hardness, repelling, and bending resistance were measured. The results are shown in Table 5.

Comparative Example 4
Using a bisphenol F type epoxy resin (jER807 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170), hardness, repelling, and bending resistance were measured in the same manner as in Example 14. The mixing ratio of the mixture of the bisphenol F type epoxy resin and the curing agent is shown in Table 5. The results are shown in Table 5.

As shown in Table 5, the cured product of the mixture of the epoxy group-terminated polysulfide polymer of the present invention and the bisphenol F type epoxy resin has no repellency and melts as compared with the cured product using the bisphenol F type epoxy resin of Comparative Example 4. The coatability on the zinc-plated steel plate was good, and the bending resistance was good.

Examples 20-26
A curing agent (Diteclar X-7906 manufactured by Daito Sangyo Co., Ltd.) was added to the mixture of the epoxy group-terminated polysulfide polymer of Examples 7 to 13 and the bisphenol A type epoxy resin, and the epoxy equivalent of the mixture and the amine equivalent of the curing agent were 1: 1. It was mixed so as to be 1, and mixed and stirred. The mixing ratio of the mixture of the epoxy group-terminated polysulfide polymer and the bisphenol A type epoxy resin and the curing agent is shown in Table 6. After curing for 5 days in a 23 ° C. and 50% RH atmosphere, hardness, repelling, and bending resistance were measured. The results are shown in Table 6.

Comparative Example 5
Using a bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190), hardness, repelling, and bending resistance were measured in the same manner as in Example 20. The mixing ratio of the bisphenol A type epoxy resin and the curing agent is shown in Table 6. The results are shown in Table 6.

As shown in Table 6, the cured product of the mixture of the epoxy group-terminated polysulfide polymer of the present invention and the bisphenol A type epoxy resin has no repellency and melts as compared with the cured product using the bisphenol A type epoxy resin of Comparative Example 5. The coatability on the zinc-plated steel plate was good, and the bending resistance was good.

The cured product obtained by curing the epoxy group-terminated polysulfide polymer of the present invention with a curing agent has high flexibility, excellent water resistance, chemical resistance, and weather resistance, and further has high adhesive strength. The cured product obtained by curing the epoxy group-terminated polysulfide polymer of the present invention can be used as an adhesive, a sealing material, a potting material, a coating material, a resin modifier, a primer and the like.

The epoxy group-terminated polysulfide polymer of the present invention is, in particular, a civil engineering / building adhesive, a civil engineering / building coating material, a civil engineering / building primer, an electric / electronic adhesive, an electric / electronic potting material, and a vehicle adhesive. , Can be used as a vehicle primer.

Claims (4)

Epoxy group-terminated polysulfide polymer represented by the following general formula

(However, the total of a + b + c is 3 to 50, a, b, and c are independently integers of 0 or 1 to 50, d is an integer of 1 to 3, and X is 1 to 5. Yes, R ¹ is the following general formula
_{-C 2 H 4 -O-C 2} H 4 -O-C 2 H 4 -
It is an organic group represented by, and R ² , R ³ , and R ⁴ are independent of each other and have the following general formulas.

It is an organic group represented by, R ⁶ is H or CH ₃ , and e is 0 to 3. ) The epoxy group-terminated polysulfide polymer according to claim 1, which has a weight average molecular weight of 1000 to 10000. The mixture of the epoxy group-terminated polysulfide polymer according to claim 1 in which R ^{6 is H and the bisphenol F type epoxy resin.} The mixture of the epoxy group-terminated polysulfide polymer according to claim 1 in which R ⁶ is CH _{3 and the bisphenol A type epoxy resin.}