By David Benoit and Jacob Bunge 

Nelson Peltz's investment firm launched a fight against DuPont Co. to add four directors to the company's board, setting up one of the biggest battles ever initiated by an activist investor.

The showdown follows 18 months of bickering between the two sides, and pits the competing ideas of Trian Fund Management LP, one of the world's biggest activist-investment funds, against those of a 212-year-old stalwart of U.S. industry.

With a market capitalization of $67.5 billion, DuPont ranks among the largest-ever targets of a proxy fight by an activist investor. The board nominations mark the first such fight in almost a decade for Trian, which prefers to work with companies out of the public eye. Trian owns around 2.7% of DuPont's shares.

Late Thursday DuPont said its board would review Trian's nominees and "make a recommendation that is in the best interest of all shareholders." The company strongly defended its performance and governance under Chairman and Chief Executive Ellen Kullman and said that, "Despite numerous efforts to engage constructively...Trian has chosen this path with the potential to disrupt our Company at a key stage of execution against our plan."

Trian's four nominees, which include Mr. Peltz himself, will be put to a shareholder vote at the Delaware-based chemicals company, likely in April, unless the parties reach a settlement.

Trian has argued that DuPont's conglomerate structure is unwieldy and a burden on results. The activist wants to splinter DuPont's seven business lines into three companies: one aimed at agriculture and nutrition, another for industrial materials and a third for performance chemicals, which produces materials that go into things like nonstick frying pans and house paint. A breakup, Trian argues, will free those individual businesses to cut costs and better compete.

"This is, as we see it, a referendum on performance," Mr. Peltz said in an interview.

DuPont, which has a 13-person board, already plans to spin off the performance-chemicals unit, but it has said it disagrees with Trian's analysis and believes its diverse set of businesses benefit from integrated research and sales efforts.

The challenge for both sides now is to win over shareholders. Typically, the biggest investors reserve judgment until late in the campaign, often after third-party proxy advisers weigh in. Those advisers have recently supported many activists seeking minority board representation, on the theory that shareholder voices in the boardroom are unlikely to hurt.

Robert Gentry, principal at San Francisco-based investment adviser Stewart & Patten Co., said his firm has held DuPont shares for decades and generally backs management. However, he said, "dissenting viewpoints on the board could actually be a healthy thing."

Trian has already lined up support from one DuPont shareholder, the California State Teachers' Retirement System, or Calstrs. Stock analysts have been mixed, with some saying DuPont's performance doesn't justify a shareholder uprising.

DuPont stock had a 266% total return, including dividends, from 2009 through 2014, versus 159% for the S&P 500. Last year, DuPont had a 17% return, again beating the broader market, though much of that gain occurred after Trian in September went public with its argument for the company's future, a move that pushed up DuPont's stock price.

The proxy fight bucks a recent trend for activist investors. Activist firms and their targets typically prefer to avoid proxy fights, which can get expensive, time consuming, and bitterly personal.

Trian has been among the most successful activists at securing board seats without going so far as a shareholder vote. Last year, Mr. Peltz joined the board of snack maker Mondelez International Inc., and his partner Ed Garden joined the board of Bank of New York Mellon Corp., both without a proxy fight.

In Trian's last proxy fight, in 2006, it secured board seats at ketchup maker H.J. Heinz Co. After that battle, Mr. Peltz grew close with management at Heinz, which has since been sold to 3G Capital Partners LP and Warren Buffett's Berkshire Hathaway Inc.

Arthur Winkleblack, Heinz's former chief financial officer, is one of Trian's nominees to the DuPont board along with John Myers, the former chief executive officer of GE Asset Management, part of General Electric Co., and Robert Zatta, acting chief executive and chief financial officer of chemical company Rockwood Holdings Inc.

In defense of its structure, DuPont has pointed to market-beating stock returns since Ms. Kullman took over at the start of 2009 and says its board is loaded with experienced directors who are revamping the company to focus on more-profitable products. It has also noted ongoing cost cuts and share buybacks.

Trian first reached out to DuPont in June 2013. Early on, tensions ran high, according to people familiar with DuPont and Trian and letters between the two sides reviewed by The Wall Street Journal.

Trian felt that DuPont and its advisers, Goldman Sachs Group Inc. and Evercore Partners Inc., weren't seriously considering Trian's arguments. At a September 2013 meeting with DuPont representatives, Trian fielded questions about its numbers on DuPont's expenses and business lines, said people familiar with the meeting.

The meeting "exacerbated our frustration over the lack of interaction with management and/or their advisors as it was clear that despite nearly three months having passed, the analysis of Trian's work product was cursory," Trian's Mr. Garden later wrote to DuPont's lead independent director, Alexander Cutler.

DuPont and its advisers felt they evaluated Trian's proposals in detail, say people familiar with their thinking, further explaining that participants at the meeting had to be tight-lipped as DuPont was reviewing its plans for the performance-chemicals unit, but couldn't share any details at the time. A month later it announced the unit would be spun off.

Then Trian got what it felt was another slap in the face. A field trip organized by Deutsche Bank AG analysts to DuPont's Pioneer seed division, slated for November, was canceled. Trian believed DuPont tried to block the firm from attending. Other people familiar with the field trip said there wasn't enough interest from other shareholders.

In October 2013, Mr. Garden raised the prospect of board seats in a phone call with Ms. Kullman, saying if the sides couldn't reach an agreement, it should give Trian two seats.

DuPont perceived his call as an ultimatum, according to a letter from Mr. Cutler to Trian: break up, let Trian onto the board, or face a public campaign. DuPont rejected the proposal.

Meanwhile, the company announced the spinoff of performance chemicals, a unit that accounts for about 18% of revenue. Trian felt it wasn't enough, but because DuPont pledged to hit targets for growth in 2014, the investor agreed to hold fire.

Six months later, DuPont announced it would miss the guidance.

Mr. Garden again requested board representation. Mr. Cutler came back with another "No."

In September 2014, Trian released its analysis to the public and began courting other shareholder support. Talks continued, but each side remained resolute on the question of Trian joining the board.

Write to David Benoit at david.benoit@wsj.com and Jacob Bunge at jacob.bunge@wsj.com

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