The early biocides were all inorganic compounds, such as sulfur powder and copper preparations (see Bordeaux mixture) are still in use today. In 1914, Germany's I. Riem first used organic mercury compounds to control wheat smut, marking the beginning of the development of organic biocides.
In 1934, W.H. Tisdale and others in the United States discovered the bactericidal properties of dimethyl dithiocarbamate, after which organic bactericides began to develop rapidly. There are three main series of organic sulfur biocides developed in the 1940s and 1950s: thiram, dysenzine (such as dysenzinc) and trichloromethylthio dimethylcarboximide, in addition to organic chlorine, organic mercury, Organic arsenic biocides have also been developed. Most of these biocides are protective agents and have limitations in application.
Since the 1960s, more chemical types of biocides have appeared, and the most important development is the advent of systemic biocides.
In 1965, Japan developed the organophosphorus biocides Daobijing, in 1966 the U.S. developed benomyl, in 1967 the U.S. developed benomyl, in 1969, Japan developed thiophanate, in 1974 the Federal Republic of Germany developed pyraclostrobin, 1975 Tricyclazole was developed in the United States in 1977, metalaxyl was developed in Switzerland in 1977, and aluminum triethyl phosphate was developed in France in 1978. The systemic agents represented by the above have become the mainstream of the development of biocides since the 1970s. At the same time, agricultural antibiotics have also developed rapidly. Organic mercury, organic arsenic and certain organic chlorine biocides have been gradually eliminated due to toxicity or environmental pollution problems. The new generation of systemic agents has further expanded the market for biocides due to improved control effects. By the 1980s, there were more than 200 varieties of biocides. According to a survey, the world's sales of biocides reached US$2.54 billion in 1985, accounting for 18.4% of the total sales of pesticides.
In 1984, the sales of systemic biocides accounted for 44.2%, and non-systemic agents accounted for 55.8%. For nearly half a century, the development of biocides has mainly focused on the prevention and treatment of fungal diseases, but the research and development of the prevention and treatment of diseases caused by bacteria and viruses is still insufficient.